White Paper:

51402
How WDS and Parallel Beam
Spectroscopy Work

Introduction WDS provides high spectral resolution for severely

Key Words X-ray microanalysis on the scanning electron microscope overlapping peaks (10 to 80 eV), high spectral resolution
(SEM) is accomplished using either Energy Dispersive for light element (Z < 15) detection, detection limits below
• Energy Dispersive
Spectrometry (EDS) or Wavelength Dispersive Spectroscopy 0.1% for trace element detection and excellent peak-to-
• Parallel Beam (WDS). EDS developed in the early 1970’s is a flexible background ratios. The primary limitations of WDS are
Spectroscopy elemental analysis method used for qualitative and the relatively small low-energy (E < 1 keV) sensitivity and
quantitative composition determinations of solid, liquid, incompatibility with high-vacuum field emission SEM
• Qualitative
thin film and powder samples. The overlap of analyte installations.
Microanalysis
peaks in complex EDS spectra acquired from multi- Parallel Beam
• Scanning component samples is a frequent concern. Spectroscopy (PBS) uses
Electron a high performance
Microscopes wavelength dispersive
spectrometer designed to
• Spectroscopy
address these concerns.
• Wavelength It provides exceptional
Dispersive sensitivity for low energy
Spectroscopy microanalysis of particles
and defects less than 1 µm
and at low accelerating
voltages where there is
insufficient overvoltage to
excite the high-energy
K-lines traditionally used
Figure 3: Thermo Scientific MaxRay
for qualitative and
Figure 1: Overlapping peaks from ED and WD spectra Parallel Beam Spectrometer
quantitative microanalysis.
This white paper discusses the principles of WDS and
PBS and addresses the advantages of using PBS for
Commonly Overlapped Peak Problems qualitative microanalysis.
in X-ray Microanalysis
S Kα – Mo Lα – Pb Mα Principles of WDS
Na Kα – Zn Lα
Ni Lα – La Mα
Physics
Zr Lα – Pt Mα – P Kα – Ir Mα WDS is based on Bragg’s Law of X-ray diffraction:
Nb Lα – Hg Mα Bragg’s Law: nλ = 2d sinθ Equation 1
Si Kα – W Mα – Ta Mα – Rb Lα
Al Kα – Br Lα
where λ (nm) is the wavelength of interest
Y Lα – Os Mα d (nm) is the interplanar spacing of the diffractor
O Kα – V Lα θ is the angle of X-ray incidence on the diffractor
Mn Lα – Fe Lα – F Kα
n is an integer and
N Kα – Ti Lα
Ti Kα – Ba Lα E (keV) = 12.398 / λ Equation 2
B Kα – Mo Mα Note that in Equation 2, Energy (E) and Wavelength (λ)
Figure 2: Common peak overlaps in EDS Microanalysis are inversely related: short wavelengths are high energy.
Here, spectra will always be displayed with energy
increasing to the right for consistency with EDS.
 The classic derivation of Bragg’s Law is as follows. WD spectra are acquired by scanning a diffractor and
Consider that a parallel beam of X-rays of wavelength λ is detector through a range of angles. As Bragg’s Law is
made incident on a material whose structure comprises a satisfied for various wavelengths being emitted from the
precisely parallel arrangement of planes (atomic, molecular, sample, sharp peaks result. Peak width is typically from 2
or otherwise), with an interplanar spacing, d, Figure 4. to 25 eV, compared to 80 to 160 eV in EDS. High spectral
resolution leads to high peak-to-background ratio (P/B),
and P/B controls sensitivity and minimum detection limits
for both quantitative analysis and elemental mapping.
Since the angle of incidence equals the angle of
reflection, a detector or counter must be positioned at the
same angle relative to the diffractor as the incident X-ray
beam makes with the diffractor itself. Relative to the
incident beam, the diffractor is at an angle θ, and the
detector at 2θ.
In the derivation of Bragg’s Law, a parallel beam of
X-rays was assumed. In the SEM, however, use of a spot
Figure 4: Derivation of Bragg’s Law or high magnification raster means that the beam starts
essentially at a point and diverges on its way to the diffractor.
If a flat crystal were used, the diverging X-ray beam from the
X-ray 1 is reflected into 1' from the top plane in the sample will reflect off of the crystal toward the detector
diffractor (or “crystal”) with the angle of incidence, θ, (Figure 5-flat). The signal at the detector will be very low
equal to the angle of reflection. X-ray 2-2', being reflected because only a small subset of all the possible X-rays obey
from the lower plane, travels an extra distance in the Bragg’s Law and strike the detector. This geometry was recog-
material equal to d • sinθ + d • sinθ. For an intense diffracted nized as highly inefficient and modifications were considered.
beam to result at the detector, wave segments 1' and 2' In order to increase the X-ray detection efficiency, this
must be in phase; which, in turn, requires that the extra diverging beam needs to be converged onto the detector.
path length traveled by wave 2-2' must be an integral The traditional method to converge the X-ray beam is to
number of wavelengths: that is, 2 (d• sinθ) must equal nλ. physically curve the crystals to modify the X-ray paths
If Bragg’s Law is satisfied, the emerging waves will onto a small area on the detector, Figure 5 Johann. In this
add in strength. If not, destructive interference occurs, arrangement, the sample (S), crystal, and detector (D)
with one wave cancelling another. Only a very weak beam must all lie on a Rowland circle of radius R/2. In this
or no beam will result. As the crystal is scanned through geometry, the distance from the source to the crystal (L1)
an angular range, the diffractor becomes a highly reflective and from the crystal to the detector (L2) are identical, L.
mirror only at the specific Bragg angle; the specificity of This converging ability, unfortunately, is only optimum for
the angle of high reflectivity is the key to the high spectral a single Bragg angle. This means that the intensity will
resolution of WDS. drop as the geometry varies from the optimum angle. To
combat this performance drop, the surfaces of the crystals
can be mechanically polished to the necessary curvature,
R, Figure 5 Johansson. This polishing provides a true
focusing effect and the X-ray intensity is maintained for
the whole angular working range of the spectrometer.

Flat Crystal Johann Johansson

>β β <β β β β β
d d
β β

R R/2 R R/2
S D S D S D

Focal Circle
Radius = R/2
Figure 5: Basic curved-crystal dispersion arrangements. Here, R is the radius of curvature of the crystal.
 There is still a limitation on the available energy range
possible for a single analyzer crystal due to the limited
angular range that is mechanically possible. In practice
E2 to cover a wide energy range useful for microanalysis
E3 applications, at least 3 and up to 8 crystals may be used
E1 in a spectrometer.
A disadvantage of WDS is that the spectrometer is
R open to the vacuum system of the electron microscope to
1
which it is attached. Since it can have a substantial volume,
2 pumping of the microscope column may be affected. This
R/2 3 is unlike an EDS type detector where the cryogenic
environment of the solid state detector is encapsulated and
does not have a direct opening to the vacuum system.
β1 β2 β3

Multi-element WDS
In recent years EDS detectors have improved significantly
L1 in both spectral resolution and in peak shape. Even with
L2
L3
this improved resolving capability, many X-ray lines produce
severe overlaps in spectra from EDS detectors with
Figure 6: Reflection curved crystal resolutions better than 129 eV at MnKα. Deconvolution
routines, while highly accurate, still leave some doubt as
In order to use Johansson crystals over a wide range to the actual qualitative analysis of the EDS spectra and
of angles, the geometry must maintain a constant will occasionally misidentify peaks.
Rowland Circle. This means that the L1 distance must One technique to overcome the problem of overlapping
vary with angle. In practice this change in L1 distance peaks is to operate the microscope at voltages in the range
occurs in a straight line away from the sample. In this of 30 to 40 kV and analyze the X-ray lines above 10 keV.
scheme, the sample remains fixed, the crystal location and This technique is often undesirable due to potential sample
rotation changes and the detector location and rotation damage, and the added complexity of the analysis. In
changes so that all items remain on the Rowland Circle addition, overlaps in the EDS spectra still exist at low
as the energy range is scanned. energies from L, M or N lines.
The X-ray sensitivity is highly dependent on the solid A preferred method of eliminating the question of
angle of the spectrometer. Which is the total sample angle overlapping peaks is to use a detector that provides high
covered by the analyzer crystal at the desired Bragg spectral resolution at lower microscope voltages. The
condition. At high energies, the crystals need to be at a Thermo Scientific IbeX multi-element WD spectrometer
short L. The benefit of this is that the solid angle is provides more than ten times the resolving power of even
relatively high. The disadvantage is that a large hole is the best EDS detector, and allows for easy analysis of
needed in the SEM chamber into which the crystal must difficult overlaps.
move in order to meet this short L distance. At low
energies, the L distance must increase to such a large
extent that the solid angle, and therefore sensitivity, drops
to low values.

Figure 7: Thermo Scientific IbeX Multi-element

WD Spectrometer
Page 3 of 10
 In the IbeX spectrometer, L is fixed, and the diffractor
simply rotates to achieve the desired angle with the incident
beam. It is the elimination of the L movement that gives
the multi-element spectrometer its defining characteristics.
The fixed L:
• Permits easy interfacing to nearly any SEM chamber. Since
the crystals do not enter the chamber, which is necessary
for very small L, even very small ports can be used.
• Reduces the housing size considerably because a small L
design is used. The multi-element spectrometer is about
one-third the weight and half the linear dimensions of
full-range units.
Figure 8: Multi-element spectrometer motion
• Reduces mechanical complexity and therefore cost.
The multi-element spectrometer is less than the price of
fully-focusing units. The spectrum in Figure 9, from albite, was obtained in
a multi-element spectrometer by scanning the TAP crystal
• Restricts its application to specified elements or energy
ranges. Although focusing is exact for only one energy optimized for Al through an angular range of about 12°.
per crystal, small errors in L can be tolerated, which
means that good performance can be maintained over
several degrees of scanning.
For the elements designated (one per crystal), expected
WDS performance is achieved. For the light elements,
performance may even be superior to fully focusing units,
because an optimized diffractor can be used for each
element designated.
In the IbeX spectrometer, L is typically 20 or 25 cm
(8 or 10") depending on the SEM chamber size. Up to six
diffractors can be used in a given spectrometer, each
optimized for a specific element by selection of the best
material and d-spacing, and then curved to the radius
required by the focusing equation. Each diffractor will be
curved to a different radius (correct for focusing its
designated element). Each diffractor, therefore, is on a
unique Rowland Circle. The spectrometer permits
selection of the diffractor and its rotation to a specified
Figure 9: Multi-element spectrometer motion
angle or through a range of angles. The detector (a flow
proportional counter) moves along an arc, maintaining a
constant detector-to-diffractor distance (L2=L), to its 2θ The improved resolution and peak-to-background
position (see Figure 8). Further, if the diffractor is rotated over EDS, despite moving off the focusing condition, is
to an angle other than the one for the crystal’s designated significant. Note that despite the higher Si concentration,
element, Bragg’s Law can be satisfied, but not the focusing the Al and Si peak heights are nearly equal, due to the
equation (since θ changes, but both R and L are fixed). diffractor being optimized, in this case, for Al. Crystal
Consequently, multi-element spectrometers can be scanned radius plays a significant role in the relative peak heights
through an angular range to pick up other X-ray lines, but obtained with this type of spectrometer.
will suffer loss in performance as the angle deviates from Achieving Required Motions in Multi-element WDS
the optimum. The larger the deviation, the less results
Wavelength spectrometers require precise and repeatable
compare favorably with fully-focusing systems.
mechanical movements. Conventional spectrometers
Fortunately, however, for moderate scanning ranges,
utilize complex mechanical linkages to achieve the relative
reasonable performance is achieved.
motions of crystal and detector; such linkages are fragile,
require frequent adjustment, must be moved slowly and
are prone to some degree of backlash. The IbeX
spectrometer eliminates these linkages, utilizing two
in-vacuum encoded brushless servomotors to independently
position the crystal and detector under computer control.
Such motion is referred to as positioning by independent
parameterization.

Page 4 of 10
Principles of Parallel Beam Spectrometry In PBS, a special collimating optic is placed close
Breaking from traditional WDS technology, the Thermo (20 mm) to the surface of the sample. Divergent X-rays
Scientific MAXray Parallel Beam Spectrometer uses an passing through this optic are converted into a parallel
X-ray path design that incorporates a focusing optic that beam. The MAXray PBS utilizes one or two focusing
transforms the divergent X-ray emissions from the sample optics to collect and collimate X-rays: a grazing incidence
into an intense, focused parallel beam. The beam then X-ray optic or a hybrid which combined both grazing
undergoes Bragg diffraction using one of up to six diffractor incidence and polycapillary optics. The role of these optics
crystals. This unique arrangement of optics and diffractors is to convert the naturally diverging beam into a parallel
creates a new category of wavelength spectroscopy called beam. This permits the use of flat analyzer crystals and
Parallel Beam Spectroscopy (PBS). On SEM’s, WDS provides removes the need to change the spectrometer L1 and L2
dramatically better spectral resolution and sensitivity than distances (see Figure 11). The optics can be thought of as
its energy-dispersed (EDS) counterpart, PBS in turn provides parabolic reflectors where the sample is mounted at the
significant gain improvements over WDS. focal point. The advantage of this geometry is that the
solid angle (effective detection angle) of the system is
markedly increased. The grazing incidence optic is
Large Area effective only for low energy X-rays up to < 2.5 kV and is
Proportional Counter only used when those energy X-rays need to be analyzed.
The hybrid optic is a combination of a grazing incidence
optic and a polycapillary optic. The addition of the
polycapillary optic increases sensitivity of the spectrometer
above 2 kV with an operating range up to ~12 kV.

Electron
Flat Beam
Diffracting
Crystal

Figure 11: Parallel Beam Spectrometer enables analysis of particles and

Hybrid Optic defects smaller than 1 µm
(Polycapillary &
Sample Prior to the development of the MAXray, X-ray
Grazing Incidence)
microanalysis of particles and defects less then 1 µm has
been difficult using traditional WDS. At low accelerating
Figure 10: MAXray Parallel Beam Spectrometer
voltages, there is insufficient overvoltage to excite the
K-lines, which have traditionally been used for qualitative
and quantitative microanalysis. At low beam currents the
intensities of X-rays are very low, resulting in long X-ray
counting times or poor peak-to-background ratios. However,
the focusing optics concentrate these low intensity signals
to high enough values to make PBS analysis possible.

Page 5 of 10
Diffractors X-ray Sensors
The term “crystal” is routinely used to describe the Wavelength spectrometers almost exclusively use gas
diffractor and, in fact, the device is commonly called a proportional counters. X-rays diffracted from the crystal
“crystal spectrometer.” However, the prominence of the enter the counter and cause ionization of the contained
new multilayers, which have greatly improved light gas. A central wire runs along the height of the detector
element analysis, makes the general term diffractor more (in a direction normal to the sample-crystal-detector
appropriate. The term “crystal” implies a regular plane, parallel to the crystal width), to which a bias
arrangement or stacking of atoms or ions to form the voltage of typically +2000 volts is applied. The electrons
crystalline structure of metals and minerals. The very freed by the ionization process are then accelerated to the
efficient multilayer, in fact, are not crystals but rather wire, creating new ionizations in their path, ultimately
vacuum-deposited alternating layers of different materials. producing a current pulse that is proportional to the
The “interplanar spacing” is the thickness of the lower energy of the absorbed X-ray. As in EDS, the current pulse
atomic number “spacer,” while the diffracting planes are is converted to a proportional voltage pulse in a field-
the layers of the higher-Z material. Although both terms effect transistor (FET), amplified, converted to a digital
will be used here, “diffractor” is the preferred form. signal, and counted. Unlike EDS, however, the FET is held
The commonly used diffractors are listed in the table at room temperature, and the digitizing is done in a single
below. Since Bragg’s Law contains the quantity “2d”, channel analyzer (SCA) rather than in an analog-to-digital
diffractors are typically described by their 2d value. converter (ADC). The ADC in EDS must retain the
proportionality to the original X-ray energy, so that a
Designation Full Name 2d, A count can be stored in the appropriate channel of a multi-
PET Pentaerythritol tetrakis 8.742 channel analyzer. In WDS, resolution is achieved by the
TAP Thallium “acid” phthalate 25.9 diffractor, and the SCA simply allows selection of the
W/Si Tungsten/Silicon Multilayer* 50–65 upper and lower limits of the size of the amplified voltage
Ni/C Nickel/Carbon Multilayer* 80–100 pulse that will be counted.
Mo/B4C Moly/Boron Carbide Multilayer* 140–205 Since the counter contains a gas, a window must be
used to isolate the inside of the detector from vacuum; if
*The multilayers can be manufactured to any specified 2d value, within,
approximately, the ranges shown
low energy X-rays are to be analyzed, the window must
be thin. Ultra-thin polymer windows similar to those of
The crystal d-spacing must be of the same magnitude EDS detectors are used. The detector is called a gas-flow,
as the wavelength of the X-ray to be measured. For example, or flow proportional counter (FPC). An argon-10% methane
the C Kα X-ray, at 0.282 keV, would require NiC mixture, called P-10 Gas, is the normal counter gas.
(a synthetic crystal) with a 2d value of 100 angstroms. Some fully focusing spectrometers use a dual counter
The Si Kα X-ray, at 1.74 keV, would require TAP system with the static proportional counter (SPC) directly
(a natural crystal) with a 2d value of 25.75 angstroms. coupled to and behind the flow counter. An exit window
A practical requirement in crystal selection is that in the FPC allows unabsorbed higher energy X-rays to enter
diffraction must occur within the angular range of the and be counted in the SPC. About two-thirds of the CuKα
spectrometer. The maximum angle allowed in the intensity, for example, will come from the rear counter.
MAXray is 68º, and the minimum angle is 14º. If C Kα, The speed and low noise characteristics of the
at 0.282 keV, is to be analyzed, the NiC (2d=100 proportional counter account for two additional
angstroms) is suitable. Using Bragg’s Law (Equation 1), advantages of WDS over EDS:
the C Kα peak on NiC is at 25.26º. • The counter can handle very high count rates, up to
Performance is another consideration in choosing a about 10 Kcps, without dead time, or even up to 100
diffractor. Consider one of the more involved choices, that Kcps in some cases. If the spectrometer is set to a peak
position, and say 20 Kcps can be achieved, all that
for boron, specifically, and for light elements in general.
count-rate is in the element of interest. Compare this to
EDS, which may be limited to ten thousand counts per
second over the entire spectrum.
• The counter’s low noise contributes to the excellent light
element capability of WDS. EDS detectors, which are
cooled to near-liquid nitrogen temperatures to reduce
inherent thermal noise, continue to fight that noise as
their application is stretched to even lower low-energy
thresholds.

Page 6 of 10
Detection Comparison
The following table summarizes differences among the techniques:

EDS WDS PBS Significance

Operating Principle Current induced in the Geometry and crystal Geometry and crystal Although one technique
detector is proportional to diffraction allow only diffraction allow only photons measures photon energy
photon energy. The detector photons of a particular of a particular wavelength to and the other measures
measures the photon wavelength to arrive at the arrive at the detector, which wavelength, the results are
energy. detector, which counts counts photons. It does not the same, because these
photons. measure energy. PBS uses a two parameters are directly
special optic and flat crystals, related.
and provides a larger solid
angle than WDS.

Energy Range Detector measures and Tuned to one energy at Tuned to one energy at EDS provides faster but less
counts photons of all a time. a time. accurate results, which is
energies simultaneously. The range of energies The range of energies especially useful for data-
The range of energies depends upon the number depends on the type of optic intensive analyses such as
depends on the electronics, of crystals and the angular and number of crystals, but qualitative analyses,
but is typically 0 – 40 keV. range of the spectrometer. is typically 0 – 12 keV. element mapping, and
compound identification.

Detector Resolution EDS resolution is Resolution is limited by Resolution is limited by PBS/WDS can resolve
reduced by: calibration accuracy. calibration accuracy and peaks more precisely than
• Noise in the detector Resolution varies from 5 to crystal perfection. EDS, which is especially
signal current 25 eV and is ~20 eV for Resolution varies from useful when overlapping
manganese. ~10 eV at low energies energy peaks are a problem.
• Incomplete conversion of
photon energy to signal (<500 eV) to ~45 eV
current for manganese.
• Resolution varies from
~50 eV for carbon to
~129 eV for manganese

Deadtime Deadtimes are longer than Deadtimes are short Deadtimes are short Higher throughputs are
those for WDS, typically by because the detector only because the detector only possible with WDS.
a factor of 10 to 100 times, needs to count, not needs to count, not
because of the additional measure, photons. measure, photons.
processing needed for the
measurement.

Element Restrictions Detects all elements having Detects all elements having Detects all elements having Both EDS and WDS can
atomic numbers greater atomic numbers greater atomic numbers greater detect all elements except
than or equal to beryllium, than or equal to beryllium, than or equal to beryllium, hydrogen, helium, and
depending on sensor and depending on the crystal depending on the optic and lithium.
window materials. selection. the crystal selection X-ray.

Detection Limits Roughly on the order of 1.0 Roughly on the order of 0.1 Roughly on the order of 0.1 Use WDS for trace element
to 0.1 weight percent to 0.01 weight percent, to 0.01 weight percent, analysis.
depending on the (lower) depending on the (10 x depending on the (10 x
element peak-to-background better) element, peak-to- better) element, peak-to-
ratio, the detector, the background ratio. background ratio.
sample, and other conditions.

Solid Angle Comparison Medium (1-15 millisteradian) Small (0.6 ~ 2 millisteradian) Large (12-184 millisteradian), PBS has the best solid
Tungsten SEM, LV, Nature, depending on the energy dependent on X-ray energy angle and has the lowest
VP, Environmental, cold and diffractor. Tungsten Tungsten SEM, cold FESEM, beam current requirements.
FESEM, thermal FESEM, SEM. thermal FESEM, EPMA. Thermal FESEM, EPMA.
EPMA.

Page 7 of 10
Comparison of EDS, PBS Maxray-ER and Element Specific WDS IbeX
Element Resolution (eV) Count Rate (cps/nA)* Peak-to-Background** MDL***
EDS Maxray-ER IbeX EDS Maxray-ER IbeX EDS Maxray-ER IbeX EDS Maxray-ER IbeX

B-Kα 53 6 8 94 396 172 57 151 568 1420 426 1050

Si-Kα 81 8 11 309 264 77 85 796 50 641 227 3070
Mn-Kα 131 45 19 21 150 85 38 180 32 3660 633 3640

All detectors were mounted for a 30 degree take-off angle. EDS and Maxray data were collected using typical SEM conditions of 20 kV, 0.75-1.5 nA.
IbeX data was collected at 10 kV and various beam currents and had an L1 distance of 25 cm. The EDS detector was a 10 mm2 Si(Li) mounted at 55 mm
sample-to-detector distance and used a 65 µs time constant.

* Count rate is measured as the net peak x-ray detection rate per live time second per collection beam current
** Peak-to-Background is measured as the ratio of the net peak x-ray counts to the background x-ray counts far from any peaks.
*** MDL = 3.29 / (t*Rate*Current*PB)1/2
Where:
t time of typical SEM acquisition (100 sec)
Rate Count rate per nA (peak dependent)
Current Beam Current of a typical SEM acquisition (10 nA)
PB Peak-to-Background ratio (peak dependent)

Standard MAXray
Elemental Accel. FWHM Intensity MDL
Spectral Line Standard Diffractor Voltage (kV) (eV) (cps/nA) P/B (ppm)
Be Kα Be MoB4C-200 10 10 300 72 71
B Kα B MoB4C-200 10 16 4000 40 26
B Kα B NiC-80 10 9 1300
C Kα C NiC-80 10 15 2800 70 24
N Kα BN NiC-80 10 19 50 8 520
N Kα BN WSi-60 10 14 40 16 411
O Kα SiO2 WSi-60 10 18 330 90 60
Al Kα Al TAP 10 20 300
Si Kα Si TAP 10 25 200 250 47
Si Kα Si PET 10 8 100 500 47
Si Kα Si PET 20 8 230

Measurement Parameters the same as listed on Document 970A139540 (B)

Data acquired by J. V. Howard between 7 October 2005 and 9 November 2005, using the Demo MAXray on the JEOL 6400 SEM.
Reference data in engineering notebooks JVH57 pages 112 - 125, and JVH58 17-54

Page 8 of 10
 UHV MAXray-ER
Hybrid Optic with Isolation Window

Accl. MAXRAY-SEM MAXRAY-FESEM

Line Energy Specimen Voltage Diffractor Resolution Intensity Peak MDL#1 MDL#2 Proline-20 Intensity Moxtek SPC
(keV) (kV) (FWHM-eV) CPS/nA Background (PPM) CPS/nA CPS/nA
BeKα 0.108 Beryllium 5 MoB4C200 11 546 69 54 758 546 470
B Kα 0.185 Boron 5 MoB4C200 16 5000 56 20 278 5000 5781
B Kα 0.185 Boron 5 NiC-80 9 1100 43 48 677 1100 1272
C Kα 0.282 Carbon 5 NiC-80 16 3000 113 18 253 3000 2329
N Kα 0.392 BN 5 NiC-80 19 62 5 591 8357 62 39
N Kα 0.392 BN 5 WSi-60 15 42 8 568 8027 42 26
N Kα 0.392 BN 5 CrSc-80 16 530 20 101 1429 530 331
O Kα 0.523 SiO2 5 WSi-60 17 208 40 114 1613 208 145
O Kα 0.523 SiO2 5 TAP 6 37 582 71 1003 37 26
F Kα 0.677 CaF2 5 WSi-60 21 177 21 171 2413 177 141
F Kα 0.677 CaF2 5 TAP 10 27 216 136 1927 27 22
Ni Lα 0.851 Ni 10 TAP n/a 77 202 83 1180 77 67
MgKα 1.254 Mg 10 TAP 25 207 168 56 789 207 193
Al Kα 1.487 Al 10 TAP 21 485 241 30 430 485 460
Si Kα 1.74 Si 10 TAP 26 416 255 32 452 416 404
Si Kα 1.74 Si 10 PET 8 264 796 23 321 264 256
S Kα 2.307 FeS2 10 PET 14 55 323 78 1104 55 52
Ti Kα 4.51 Ti 10 PET 43 27 73 234 3314 27 26
Ti Kα 4.51 Ti 10 LiF 23 48 180 112 1583 48 46
Ti Kα 4.51 Ti 20 LiF 23 307 404 30 418 307 292
Fe Kα 6.403 Fe 20 LiF 46 147 193 62 874 147 140
Cu Kα 8.046 Cu 20 LiF 62 59 112 128 1810 59 56
Cu Kα 8.046 Cu 30 LiF 62 159 157 66 931 159 151
Ge Kα 9.885 Ge 20 LiF 79 15 53 369 5218 15 14
Ge Kα 9.885 Ge 30 LiF 79 51 90 154 2172 51 49

Notes: Intensity specifications for different

*Peak to Background Points calculated using JEOL rules: GFPC windows. For Be, B, C, N, and O
For Elements on LiF +/- 2/3 (Kb-Kα) lines – these specifications are based on
For Element on PET, TAP +/- 3/2 (Kb-Kα) experimentally determined attenuation
For Elements on Multilayers +/- lambda/5 for one SPC and one PEA9 window.
**MDL Calculation from Ziebold Equation Above 600eV – theoretical attenuation
MDL#1 – “Typical” WDS Conditions – 1000 sec, 100nA curves used to predict intensity.
MDL#2 – Possible FESEM Conditions – 100 sec, 5nA
***Time required to obtain 0.1% sensitivity at 5nA Beam Current.
Also Note: The MAXray spectrometer was inclined at 30 degrees, and all specimens were horizontal.
The MAXray spectrometer currently only has a Flow Proportional Counter (efficiency at 8kV about 40%).
Both the Taylor and the MAC standards blocks were used to collect this data.
Intensities and P/B were determined by counting 100 seconds at the peak channel and 100s at each of the
two background points (single channel).
All data obtained above at the same conditions – i.e. Resolution, peak/background, and intensity
data is not dependent upon a slit setting (no slit used in MAXray).

Implications of the Nature of PBS:

• Compared with EDS, resolution is typically an order of • Due to the serial nature of spectrum acquisition,
magnitude better; peak overlaps are virtually eliminated qualitative analysis is slow compared to EDS
• The high resolution leads to order-of-magnitude better • The large solid angle achieved using the PBS optic yields
sensitivity than EDS. The sensitivity improvement is a greater sensitivity to light element energies than
often most dramatic in the light element region conventional WD
• The better P/B and elimination of overlaps yield more • WDS is often operated by driving the crystal directly to
accurate quantitative analysis for those elements in low the peak, with or without peak searches. In this manner,
concentration or involved in the overlap the counting time is devoted only to the points of real
• Because the WD spectrometer can be positioned at the interest. For minor elements, WDS then becomes fast
center of the peak, where P/B is maximized, WDS relative to EDS, which spends most of its time counting
provides superior X-ray maps, especially for low X-rays from the major elements
concentrations
Page 9 of 10
WDS Applications Analysis of Boron In BPSG
A few typical examples of WDS applications, from both BPSG (borophosphosilicate glass) is a thin film used in the
types of spectrometers, are given in the following sections. semiconductor process. It is important to control both the
P and B “dopant” levels to insure proper device yield and
Resolution of W, Ta, and Si product reliability. WDS is one of the best methods for
Another common overlap area in EDS is the Si K with the boron determination in BPSG because of its high analytical
W and/or Ta M lines. The Si Kα is at 1739 eV, while the sensitivity for light elements and its straight forward linear
W Mβ is at 1774 eV, and the Mα at 1835 eV. Less than response (in this application) to the boron concentration.
100eV separate these three peaks. Ta and Si present an The IbeX spectrometer is used in the industry to perform
even more severe overlap, with the two Ta M lines the analysis; with the Mo/B4C multilayer, it is the most
bracketing the Si peak by 30 eV on the low side and efficient and cost-effective WD system available. Figure 13
25 eV on the high side. (top) shows an overlay of 4% and 2% BPSG. In the actual
A difficult analytical problem is found in the analysis analysis, however, peak scans are not done; rather, the
of thin Ta- or W-Si films used in the semiconductor spectrometer is simply driven to the B peak position, where
manufacturing process. Since these films are produced on counts are recorded for standards and unknowns. A typical
Si wafers, Si emission from the substrate can overwhelm the (linear) calibration curve is shown in Figure 13 (bottom).
Si and Ta or W peaks from the film. To avoid significant
penetration into the film, and the resulting high substrate
intensity, a low accelerating voltage (less than 10 keV)
a
must be selected. The use of the L-lines of W or Ta is thus
precluded, and the overlapped M-lines must be used for
analysis. Because of the severity of the overlap, the
quantitative precision required can only be obtained by
resolving the analyzed peaks, dictating the use of WDS.
The following figure shows spectra from TaSi and
WSi. In the WSi spectrum there is a noticeable indication
that two Si satellite lines are present just to the high
energy side of the Kα. These lines, in fact, are separated
by only 2 eV (at 1752 and 1754 eV).

Figure 12: WDS spectra from TaSi (left) and WSi (right). Note the indication of
the 2 Si satellite lines, separated by only 2 eV, in the WSi spectrum.

Figure 13: (a) 4% B BPSG spectrum overlaid with 2% BPSG spectrum,

(b) Calibration curve for B in BPSG.

Page 10 of 10
Resolution of Ba and Ti Conclusion In addition to these
offices, Thermo Fisher
BaTiO3 is a dielectric material that is used for a number of EDS measurements are fast, efficient, and straightforward
Scientific maintains
purposes in a variety of electronics applications. Being because the whole energy spectrum is collected in parallel.
a network of represen-
able to confirm that both elements are present in a sample When used in conjunction with computer automation, it
tative organizations
is paramount for proper material performance. Because provides a powerful analytical tool for determining elemental
throughout the world.
the primary x-ray lines of both the Ba-L and the Ti-K line composition in solid, powder, thin film and liquid samples.
families are separated by less than 50 eV, there is a heavy EDS has found wide application for quality control and
peak overlap in EDS analyses when the system has a quality assurance of both intermediate and finished products.
spectral resolution greater than 120 eV at that energy. The Many process samples and environmental samples are
superior spectral resolution of the Maxray PBS ideally addressed by non-destructive EDS methods that are
spectrometer can easily resolve both peaks confirming the versatile with regard to the sample types that can be Africa
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Figure 14: WDS spectrum (red) overlaid on EDS spectrum (yellow) of the addition provides significant sensitivity improvements over India
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