1

Coating Thickness
Measurement
and Materials Analysis
Using X-Ray Fluorescence

2


How to Measure Using X-Ray
Fluorescence?
3
M L K
K-alpha
K-beta
Primrstrahlung
Elektron
0
100
200
300
400
500
4 5 6 7 8 9 10 11 12 13 14 15
E / keV
Z

/

c
p
s
0
100
200
300
400
500
4 5 6 7 8 9 10 11 12 13 14 15
E / keV
Z

/

c
p
s
Principle of X-ray
Fluorescence Analysis
(XRFA)

Excitation of atoms of the sample
material through primary X-radiation


Emission of characteristic fluorescence
radiation through excited atoms


Recording of the fluorescence
radiation and evaluation of the
spectrum

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Spectrum Example
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Which Elements Can Be Measured?
Proportional counter tube beginning with atomic number 20 (Ca)
Semiconductor detector beginning with atomic number 20 (Ca) or 13
(Al)
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Kollimator
Probe
Rntgen-
detektor
Video-
kamera
Rntgenrhre
Spiegel
Anode
Kathode
Spektrum
Au = 751,3
Operating Principle of an
X-Ray Fluorescence
Instrument
X-ray tube: Generation of the X-radiation by
accelerating electrons from the cathode to the
anode.

Primary filter: Modification of the primary
radiation.

Collimator: Limiting the measurement spot.

Detector: Measurement of the fluorescence
signal and conversion into a spectrum.

Computer: Evaluation of the spectrum and
computation of the resultant values.

Video camera: Viewing the measurement
location.
Primary filter
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X-Ray Tube

Anode materials
- Standard material is tungsten
- For special applications, other materials are used as well
(e.g., Mo, Rh)

High voltage
30-50 kV in instruments with proportional counter tubes
10-50 kV in instruments with semiconductor detectors

Standard tube (in combination with 1 collimator) and
Microfocus tube (in combination with 4 collimators)

Tube and high voltage cascade are embedded in oil.
- Optimal heat dissipation
- Reliable operation at high outside temperatures
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Excitation at Various High Voltages
Al filter:
50 kV
30 kV
Optimal excitation when HV = 2-3 times the ionization energy (energy table).

High-energy radiation components that do not contribute to the generation
of evaluable information should be avoided.
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Example: Sn-Spectra at Various
High Voltages
50 kV
30 kV
10 kV
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Primary Filter
Modification of the primary radiation

The best possible excitation, or reduction of interfering underground,
respectively, is possible by selecting a suitable primary filter.

For example, the Al filter is often advantageous in the trace analysis
of heavy metals (low background noise)

Most often, the standard filter for coating thickness measurements is
Ni
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Example: Primary Filter for the XDV-SD
Nickel 10 m
"Air"
Aluminum 1000 m (Al 1000 yellow)
Aluminum 500 m
Titanium 300 m
Molybdenum 70 m
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Example: Excitation Conditions for
Measurements of Pb Traces in Sn/Cu
Pb and Sn are excited optimally at 50 kV.
Low background for Pb-L with an Al filter
Orange: 50 kV, Ni filter

Blue: 50 kV, Al filter
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Collimator
Instruments with standard tube:
One fixed collimator (0.3 mm, measurement spot approx. 0.7 mm)

Instruments with microfocus tube:
Four collimators selectable via the software (e.g., 0.1 mm, 0.2 mm,
0.3 mm, 0.05 x 0.3 mm)

Disadvantages of very small collimators: Count rate drops, thus, infinitely
small measurement spots are not possible

Patented arrangement with a collimator made of glass allows for a short
collimator - probe distance

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Patented DCM Method
(Distance Controlled Measurement)


Automatic correction of the
reading in relation to the
measuring distance.

It is, therefore, possible to
freely select the measuring
distance within the
applicable measuring
distance range.
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Alternative X-Ray Optics
Monokapillare Polykapillarlinse
Rntgenspiegel
Kollimator
Rntgenquelle
Poly-capillary: Half widths of 20 60 m with very high count rates

X-ray mirror: Measurement spot of approx. 100 x 100 m

Application example: Chem. Au (50nm) / Pd (50nm) / NiP / Cu -PCB
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Detectors
Proportional counter High count rates through large entry window,
tube: Energy resolution ~ 900 eV (Mn-K
a
)
Advantages with simple applications such as
simple coating thickness measurements and
materials analyses

Si-PIN diode: In comparison smaller count rates through
smaller entry window,
Energy resolution ~ 150-200 eV (Mn-K
a
)
Advantages in complex applications such as
thin coatings, dental gold, trace analysis
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Comparison of Proportional Counter Tube
and Semiconductor Detector
Instrument models : XDVM

-P, XDL

,
XUL

Element range: From Z = 19
Concentration range: From ~ 100 ppm
Instrument models: XAN

, XDAL

, XDV

-
SD
Element range: From Z = 13
Concentration range: From ~ 10 ppm

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What Does the Reference Measurement Do?
In X-RAY instruments (in particular in instruments with a proportional
counter tube) the energetic position ("x-axis) of the fluorescence peak
may change over time.
Solution: New energy calibration through measurement of Ag and Cu

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How Does the Coating Thickness Measurement
Work?
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How Big Is the Measurement Range?
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Measurement Uncertainty (Accuracy)
Trueness
systematic
Precision
random
Repeatability
precision
Reproducibility
Positioning
Operator
Hardware (detector, measurement
spot, etc.)
Measuring time
Application
Calibration (adjustment)
Standard-free calibration
according to fundamental
parameters
2
Standard-supported
traceable calibration
Corrective calibration with
certified standards
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Measuring distance
Collimator
Measuring time
Coating thickness
Focusing
Positioning
Parameters Influencing the Trueness and
Precision in X-ray Fluorescence Measurements
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Meas. signal (count rate) ~ 1 / (measuring distance)
2

Repeatability precision ~ count rate
Patented DCM Method
(Distance Controlled Measurement)

Automatic correction of the reading in relation to
the measuring distance. It is, therefore, possible to
freely select the measuring distance within the
applicable measuring distance range.
Select a measuring distance
that is as small as possible
Influencing Parameters in X-ray Fluorescence
Measurements: Measuring Distance
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Influencing parameters in X-ray fluorescence
measurements: Collimator / Measurement Spot



Measurement signal (count rate) ~
(diameter measurement spot)
2

Repeatability precision ~ count rate
Small measurement spots
allow for the best determination of
inhomogeneities

Large measurement spots
Low influence of inhomogeneities on
the result

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Influencing Parameters in X-Ray Fluorescence
Measurements: Measuring Time
Often very long measuring times are not useful; in such cases it is
better to form a mean value of several measurements instead of
longer measuring times.
Repeatability precision ~ measuring time
A four times longer measuring time improves the
repeatability precision by a factor of 2
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Example:
Copper
on
iron (30 s)
Influencing Parameters in X-Ray Fluorescence
Measurements: Coating Thickness
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Influencing Parameters in X-Ray Fluorescence
Measurements: Focusing of the Sample
The sample - detector distance must be known to the software.

Implementation at Fischer via camera with a low depth of field

Focusing either manually or via auto-focus

Exception: Ratio method (proportion method)
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Influencing Parameters in X-Ray Fluorescence
Measurements: Measuring on a Slanted Plane
Theory: Trigonometry

Practice: Shadow effects play a role
as well, thus, if possible always
position horizontally.

th
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Influencing Parameters in X-Ray Fluorescence
Measurements: Measuring on Cylindrical Objects
Sample orientation depends on the position of the detector in the
instrument.
Background: From the viewpoint of the detector, the x-ray should strike
the sample as vertically as possible.
The example below refers to instruments, where the detector is located
to the left of the measurement beam (XDL

, XDVM

-P, XDAL

, XDV

-
SD).
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Influencing Parameters in X-Ray Fluorescence
Measurements: Shadow Effect
The detector must have an "unobstructed view" of the measurement spot.
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Selected Applications
Monitoring of measurement devices
Coating thickness measurement
- Electroplated coatings
- Measurement on wires
- Zinc lamella coatings and adhesion promoting layers
- PVD coatings
Materials analysis
- Gold analyis
- Stainless steel, brass analysis
Bath analysis
RoHS
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Monitoring of Measurement Devices
Regular
measurements of a
reference sample or
of a calibration
standard in a
control chart

Control is activated
when reaching the
warning limit
(reference
measurement or re-
calibration).
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Electroplated Coatings
As a rule, electroplated coatings can be measured without problems.
In actuality, XRFA measures mass per unit area [mass / area].
Coating thickness = mass per unit area / density
The densities of the pure elements are stored in the software.

Sometimes a manual density adjustment is required,
e.g., for gold:
Fine gold: 19.3 g/cm
3
Hard gold: e.g., 17.5 g/cm
3
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Typical Application Examples:
Electroplating service industry
- Screws, fasteners, etc.,
- Zn/Fe, ZnNi/Fe, Ni/Fe, etc.
- Standard collimator of 0.3 mm is often sufficient
Pc-board industry
- Chem. Au/NiP/Cu/PCB, chem. Sn/Cu/PCB
- Au/Ni/PCB, Sn/Cu/PCB, Ag/Cu/PCB
- At times rather thin coatings and small measurement spots
- Programmable stage recommended
Connector contacts
- Au/Ni/Cu alloys, Sn/Ni/Cu alloys, etc.
- Often curved surfaces
- At times very small measurement spots required
- Programmable stage recommended
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Coating Thickness Measurement on Wires
The diameter of the wire should be 3 to 6 times larger
than the measurement spot. Advantage: Regular
calibration standards can be used for the calibration.
The measurement spot must outshine the wire. Wires with
a known coating thickness must be used for the calibration.
Method - plane:
Method - curved:
Measurement beam
Wire
Coating
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Zinc Lamella Coatings and Adhesion
Promoting Layers
In principle, these coatings consist of metal particles / lamellas
(e.g., Zn, Ti) in an organic matrix.

For the measurement, a separate adapted measuring application
will be required for each system (manufacturer, product).

The calibration must be carried out using fitting calibration
standards, which - as a rule - must be made by the customer.
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PVD Coatings (CrN, Etc.)
Hard Material Coatings (TiN, Etc.)
Actual samples that have been measured using an alternative method
(e.g., polished dome sections) must be used for the calibration.
E.g.: CrN, TiN, TiAlN, TiCN
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Materials Analysis Gold, Stainless Steel, Brass
- A proportional counter tube is sufficient for simple
requirements (e.g., positive material identification).
- The best precision is achieved using the Si pin diode.
- Depending on the X-RAY model, a repeatability precision of
up to 0.05 % is possible for gold.
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Bath Analysis Using
X-Ray Fluorescence Spectroscopy
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1. Measuring cell - bottom
2. Edge of beaker
3. Beaker
4. Reference board
5. Clamping ring
6. Drip groove
7. Cover foil
Structure of the measuring cell
Bath Analysis Using XRFA
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Filling the Measuring Cell
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Solution Analysis
XAN mg/l XDVM-W mg/l
Ni 26 33
Cu 15 53
Zn 11 35
Ag 42 47
Sn 71 95
Au 19 19
Pb 24 48
Special solution measuring cell:
Fluorescence radiation of the rear
wall provides information about the
matrix of the solution (Cl, SO
4
, CN,
...)
Standard deviation for some
metals at a measuring time of
30s.
Primrstrahl
Dnne Folie
Lsung
Rckwand (Mo, Ni...)
Fluoreszenzstrahlung
Special solution measuring
cell:
Fluorescence radiation of the rear
wall provides information about
the matrix of the solution (Cl, SO
4,

CN, ...)
Standard deviations
for some metals at a
measuring time of 30s.
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RoHS Conformity:

What Can X-Ray Fluorescence Analysis
Achieve?
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Lead < 0.1 %

Mercury < 0.1 %

Cadmium < 0.01 %

Hexavalent chromium < 0.1 %

Polybromenated biphenyls (PBB) < 0.1 %
Polybromenated diphenyl-ether (PBDE) < 0.1 %

Limit Values
The more homogeneous the material!!!
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What Can Be Measured Using XRFA?
All elements from atomic numbers 13 -17 (Al - Cl) to 92 (U)
Only the respective element (type of atom) can be determined.
Providing information regarding chemistry such as oxidation
level or whether the element is part of a compound is not
possible.
Thus, the total element content is determined.
I.e., the PBB or PBDE concentration cannot be measured
specifically, rather only the total bromine concentration.
I.e., chrome(VI) cannot be detected qualitatively or
quantitatively. If the total chrome concentration is < 0.1 %, the
chrome(VI) concentration is also < 0.1 %.
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Implementation at Fischer - XDV-SD or XAN-DPP
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Example:
Automatic Scanning of Pc-Boards
Instruments with a
programmable XY(Z) stage
can record the element
distribution on a pc-board.
For example, Pb can be
determined qualitatively in
one step.
Thereafter, quantitative
measurements are made at
the suspicious locations.
The image to the right shows
the lead distribution on the
pc-board.
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Example:
Analysis of Solder
Pb in solder or in
solder layers

Electroplated solder
layers
Hot air solder leveling
Solder ("wave")
Solder paste
Manual solder pads

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X-RAYs With Proportional Counter Tubes
XUL

/ XULM

Samples with simple
shapes
Manual sample
positioning
Pc-boards, contacts,
wires, contract
electroplating plants


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X-RAYs With Proportional Counter Tubes
XDL

/ XDLM

Samples with complex shapes
Measurement at a distance
(DCM)
Auto-focus
Manual or automatic sample
positioning
Standard instrument with many
electroplatings
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X-RAYs With Silicon Pin Diodes
XAN

Analysis instrument, also
coating thickness
measurement
Manual sample positioning
Large measurement spots
Analysis of gold and
precious stones, RoHS


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X-RAYs With Silicon Pin Diodes
XDAL

Coating thickness + analysis
Auto-focus
Programmable stage
Complex coatings, thin
coatings
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X-RAY With Silicon Drift Detector
and X-Ray Capillary
XDV

-
Measurements on fines structures
X-ray capillary
Very high count rates
Short measuring times
Very good repeatability precision
Measurement spots
20 60 m (fwhm energy-dependent)
High-precision programmable stage
Semiconductor detector
Good energy resolution
Application:
Lead frames, pc-boards
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X-RAY With Silicon Drift Detector
XDV

-SDD
Better energy resolution 140
eV
Samples with fine structures
High-precision
programmable stage
Small and large
measurement spots
Digital pulse processor
High-end applications, RoHS
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X-RAYs With Silicon Drift Detector
XUV

-773
Measurement and analysis
of thin coatings
High-precision
programmable stage
Analysis in air, helium or in
vacuum
Exchangeable apertures
Six primary filters
Detection of up to 24
elements
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In-Line Measurement
CONTI 4000
Measurement and analysis in
the manufacturing process
High-precision programmable
stage
Fast travel device
Samples with fine structures
Small measurement spot

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In-Line Measurement
CONTI 5000
Specifically for applications
in the solar industry
Can be integrated in
production plants
Measurement and analysis
in air or in vacuum
Measurement also on very
hot surfaces
Silicon PIN detector

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Fischerscope X-Ray "MC" - Modular X-Ray
Systems for Inspecting Large Workpieces
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The Modular Solution "MC" Additional Sizes
L x D x H in mm:
1500 x 1000 x 1100
2205 x 1000 x 1100
2910 x 1000 x 1100
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Summary
The X-ray method is non-destructive, fast and versatile in its
use.
Very reliable and precise measurement method
Low influence of external conditions (shape, etc.)
The measurement data are evaluated using data processing,
are passed on and documented.
Instrument operation is user-friendly and can often be carried
out by untrained personnel.
A comparison with other methods shows the superior cost-
effectiveness of the method.