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Practical Spectrum Imaging:Rapid Collection for Routine Analysis

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Welcome

Don BeckerWebinar Host

Today’s TopicsIntroductionX-ray Detectors for MicroanalysisHyperMap ApplicationsμXRF Instrument Design - ARTAXARTAX Element Mapping in Forensics and IndustryQ&A

Guest SpeakersTed Juzwak – Applications Lab Manager, Ewing, NJArmin Gross – International Sales Manager, Berlin, Germany

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Bruker Companies

Bruker AXSAdvanced X-ray Solutions

XRF, Diffraction, Single Crystal, Microanalysis

Bruker DaltonicsMass Spectrometry

Bruker OpticsFTIR, NIR, Raman

Bruker BioSpin(Affiliated privately held not part of Bruker BioSciences)

NMR, EPR, MRI

Bruker BioSciences Corporation(NASDAQ: BRKR)

The innovative ultraflex™ III mass spectrometer

S4 Pioneer

D8 Discover

Recombinase Fragment with 3 DNA Strand – Dr. Yu Lau, University of Saskatchewan

XFlash 4010

TENSOR 27 & HYPERION FT-IR Microscope

AVANCE III

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Bruker AXS Microanalysis

MicroanalysisEst. 2006

Est. 1965

Est. 1991

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MicroanalysisQUANTAX with XFlashQUANTAX with XFlash®

Ted JuzwakBruker AXS Microanalysis USA

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UHV Dewar Si(Li) Detector XFlash® Detector

Conventional EDS Detector

Cooling with LN2 (ca. -190°C)

2 hours to cool down

Technology from 1960’s

Weight approx. 8 kg

SDD Technology

no LN2 (Peltier cooling, ca. -25°C)

30 seconds to cool down

Up to 10 times faster

High efficiency

Stable resolution, reliable quantification

Weight 2.5 kg

X-ray Detectors for Microanalysis

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History of the SDD

2nd generation

XFlash®20002000

2007: 10th anniversaryof the XFlash® Detector!

XFlash®30012002

3rd generation

1st generation

XFlash®10001997

4th generation

XFlash®4010July 2006

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4th generation high resolution detector

10 mm² active area

Energy resolution: ≤ 125 eV,

specification at MnKα, 100 000 cps

Detection of beryllium (4)

Input count-rate: > 700,000 cps

2-stage Peltier cooler

Vibration-free

Maintenance-free

XFlash® Detector 4010

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129eV Resolution at Mn: XFlash vs Si(Li)

0-2 129 1292-8 131 1298-14 133 12914-20 138 12920-42 149 12942-62 161 12962-110 191 129110-150 NP 129150-200 NP 130200-300 NP 131

Count Rate (Kcps) Si(Li) XFlash®

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XFlash 4010 SDDResolution vs Count Rate

Resolution vs. Count Rate100

120

140

160

180

200

220

2405 10 20 40 63 100 140

Count Rate [kcps]

Reso

lutio

n [e

V]

Si(Li)Xflash

11

0

10

20

30

40

50

60

70

80

90

100

110

120

130

140

150

160

0 50 100FWHM, elektronic [eV]

FWHM [eV]

CuNiCoFeMnCrVTiScCaKArClSPSiAlMgNaNeFONCBBe

-8 eV at

Mn/Kα

-17 eV at

C/Kα

Theoretical energy resolution ofKα lines for Si-based detectors

Mn/Kα=133 eVMn/Kα=125 eV

C/Kα =65 eV

C/Kα=48 eV

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XFlash SDD at 5K, 10K, 20K, 50K, 100K cps

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5K, 10K, 20K, 50K, 100K cps –No peak shift with count rate!

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Output Count Rate vs Input Count Rate

Output Count Rate (OCR) versus Input Count Rate (ICR)for selected shaping times (SVE III)

0

100

200

300

400

0 100 200 300 400 500 600 700 800 900 1000

Input Count Rate [kcps]

Output Count Rate[kcps]

"275kcps"

"130kcps"

"60 kcps"

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XFlash® Family Of Detectors

XFlash 4010: 10mm2, 125eV, Be DetectionXFlash 4030: 30mm2, 133eV, B Detection

XFlash Quad 4040: 4 x 10mm2, 125eV, Be Detection

XFlash Multi- Detectors

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Multiple Detector Systems

Internal view chamber

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Si(Li) detector (30 mm2)• 138 eV resolution• 20,000 cps input• 60% dead time • Duration: 6.25 hours

XFlash® QUAD 4040• 138 eV resolution• 720,000 cps input• 40% dead time• Duration: 7 minutes

Mineralogical sample, 15 keV, 600 x 450 Pixel

The 30 mm2 Si(Li) needs 50x longer for the same result!

Comparison: XFlash® with Si(Li)

Note: For an XFlash 4030 a 30mm2 SD, Duration = ~ 8.75 minutesand for an XFlash 4010 a 10mm2 SD, Duration = ~ 26.25 minutes

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SD Detectors have become the EDS detectors of choice

No liquid nitrogenNo vibrationReady to use in 30 secondsDoes not have to be warm to vent chamberBetter resolution than the traditional Si(Li)No change in resolution with count rate to 100,000 cpsCount rates of up to 1,000,000 cpsHigh resolution maps - Real time analysis of HyperMap Makes traditional mapping obsoleteFaster survey of sampleEasily moved to a new microscope – No Dewar!10 mm sq., 30 mm sq. active areasQUAD: 4 x 10mm sq. arrayMultiple XFlash detectors: up to four SDDs together

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Sample: Steel with Inclusions

Overall Spectrum15kV, 35oΨ, 20nA80Kcps @ 40%DT

50 µmMAG: 500X HV: 15.0 kV WD: 10.0 mm

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ESPRIT: Multi-Point Analysis

Region 1

Region 2

Region 3

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Multi-Point Analysis

50 µmMAG: 500X HV: 15.0 kV WD: 10.0 mm

Region 3

Region 2

Region 1

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HyperMap: Collection

50 µmMAG: 500X HV: 15.0 kV WD: 10.0 mm

Region 3

Region 2

Region 1

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50 µmMAG: 500X HV: 15.0 kV WD: 10.0 mm

HyperMap: SEI, Composite and Individual Maps

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Maximum Pixel Spectrum

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Verification of Maximum Pixel Spectrum

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HyperMaps: SEI and Individual Maps

50 µmMAG: 500X HV: 15.0 kV WD: 10.0 mm

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HyperMap: SEI and Composite

50 µmMAG: 500X HV: 15.0 kV WD: 10.0 mm

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Counts Area SE Fe-KA Al-K S-KA Ti-KA Mg-K P0 94.1 % -- 64.11 4.01 3.45 2.50 2.81 P1 2.5 % -- 37.45 64.09 2.75 2.15 5.18 P2 1.8 % -- 58.89 7.72 3.23 5.41 2.73 P3 1.5 % -- 46.07 39.47 3.20 2.64 3.45

AutoPhase

Counts Area SE Fe-KA Al-K S-KA Ti-KA Mg-K P0 94.1 % -- 64.11 4.01 3.45 2.50 2.81 P1 2.5 % -- 37.45 64.09 2.75 2.15 5.18 P2 1.8 % -- 58.89 7.72 3.23 5.41 2.73 P3 1.5 % -- 46.07 39.47 3.20 2.64 3.45

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AutoPhase Extracted Spectra

Area Fraction = 94.1%

Area Fraction = 2.5%

Area Fraction = 1.8%

Area Fraction = 1.5%

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XFlash®, QUANTAX & ESPRIT

XFlash SDD • No maintenance• High speed data acquisition• Maintain spectral resolution• Maintain sensitivity for all elements

Not limited to low resolution imagesCompositional image in secondsID phases that backscatter cannot separateImmediate verification of data while collecting• Meaningful Maps available in seconds• Extract spectra to verify identification and phase• Maximum pixel calculation• Phase Analysis

Full Quantification of any data

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Micro-XRF SpectrometerARTAXARTAX

A portable spectrometeroffering µm resolution

Armin Gross

Bruker AXS Microanalysis GmbH

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Contents

1. Introduction to µXRF

2. ARTAX instrument design

3. Line scan of solar cells

4. Element mapping in forensics

5. Element mapping in industry

6. Summary and outlook

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XRF TechnologiesµXRF vs EDS and XRF

Technology X-ray Microanalysis(EDS)

Micro X-rayFluorescence Analysis

(µXRF)

X-ray FluorescenceAnalysis (XRF)

Capability

Limitation

High resolution element mapping in the sub-µm range

Non-destructive spatial investigation of element distribution

Elemental analysis of bulk samples

Sample size limited by chamber

Analytical range of 10 µm to 10 mm

No information about spatial element distribution

nm - µm µm – mm mm - cm

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ARTAXIntroduction to µXRF

Micro X-ray fluorescence analysis (µXRF)

• Spatial resolved multi-element analysis

• Non-destructive analysis of the element composition

• Analysis at the location of the object

• Scan range 50 x 50 mm

• Target market art and conservation

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XFlash detector

Sample illumination

He purge

CCD camera

Collimator / Polycapillary lens

ARTAX Instrument DesignDetail of the Measuring Head

Tube housing

Red LED

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Beam focusing by polycapillary lensEnsemble of several thousand glass capillariesEach capillary ~1 µm in diameter

Advantages for fast mappingMinimal focal spot sizeabout 70 µmOutstanding intensity gain> 1000 compared to collimator

Instrument DesignExcitation Source

Metal-ceramic X-ray tubeMo, W or Rh target

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Instrument DesignExcitation Source

High precision coupling for fast exchange of excitation source

A source contains:

• tube housing incl. shutter

• X-ray tube (Mo, Rh, W target etc.)

Micro-focus tubee.g. Mo-target

Line-focus tubee.g. W-target

Polycapillary lens

Collimator

coupling

Filter device

• X-ray optics (polycapillary lens, collimator)

• Filter device

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Glass Standard BR E2Spectrum section above 20 keV

22 24 26 28 30 32 34- keV -

0.0

1.0

2.0

3.0

4.0x 1E3 Pulses

Ag

Sn

Sb

Ba

In

blue = W

green = Mo

red = Cr

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Glass Standard CRM 610Low energy range

1.00 1.50 2.00- keV -

0

200

400

600

PulsesNa_K Al_K

Na

Al Si

blue = W

green = Mo

red = Cr

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Specifications• Si drift chamber detector (SDD)• 10 mm² active area, Be window• Electro-thermal cooling

Advantages• Energy resolution < 160 eV

(Mn-Kα line, 100 kcps)

• Highest throughput (> 100 kcps)

• No liquid nitrogen required

Upgrade option• Energy resolution < 145 eV

Instrument DesignXFlash® Silicon Drift Detector

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Instrument DesignCCD Camera and Sample Illumination

• Camera image of sample area under investigation Magnification about 20

White LED for optimization of the image qualitycan be dimmed

One red laser diode - can be dimmed

Red spot in center of crosshair

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Instrument DesignHelium Purging

SpecificationsDetection of light elementsNa(11) to Ar(18)

AdvantagesNo vacuum required,avoids damage of fragile samples

Hardly limitations in form and size of the sample

Small time effort

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• 15th to 17th century: peak in the painting of enamels in thefrench city Limoges

• End of 19th century:Limoges style replicas

• Line thickness of paintings about 150 µm

• Classification initially done by EDS

Art ApplicationsLimoges Painted Enamels

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Line Scan ApplicationInvestigation of Solar Cells

Production of solar cellsTypical layer structure of a CdTe solar cellDuring production the homogenity is tested routinely

Measurement parametersARTAX line scan48 measurements50 kV, 600 µA15 s

Glass body

CdTe3000 nm

Mo 5 – 15 nm

Al 200 nm

Cr 5 nm

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ApplicationsInvestigation of Solar Cells

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ApplicationsInvestigation of Solar Cells

10

100

1000

10000

100000

18,83 19,21 19,59 19,97 20,35 20,73 21,10 21,48 21,86 22,24 22,62 23,00

X-axis (mm)

Net

are

a co

unts

Al K12 Si K12 Cr K12 Mo L1 Cd L1 Te L1

Si: lower absorbance

Cd > 90% removedTe almost unchanged

Mo ?

Al: almost removed

Cr: removed

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ApplicationsElement Mapping in Forensics

Section of a bullet

• Area 1.8 x 1.8 mm• Meas. points 100• Meas. time 5 s• Total time 23 min

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ApplicationsElement Mapping in Forensics

Section of a bullet

• Spectrum

5 10 15 20- keV -

0

2

4

6

x 1E3 Pulses

Fe Cu Zn Sr Sr Ba Pb

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ApplicationsElement Mapping in Forensics

Section of a bullet• Distribution of

Fe, Cu, Pb, Ba

39,80 39,60 39,40 39,20 39,00 38,80 38,60 38,40 38,20 38,00

33,62

33,42

33,22

33,02

32,82

32,62

32,42

32,22

32,02

31,82

198000-220000

176000-198000154000-176000

132000-154000

110000-13200088000-110000

66000-88000

44000-66000

22000-440000-22000

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39,80 39,60 39,40 39,20 39,00 38,80 38,60 38,40 38,20 38,00

33,62

33,42

33,22

33,02

32,82

32,62

32,42

32,22

32,02

31,82

198000-220000

176000-198000154000-176000

132000-154000

110000-13200088000-110000

66000-88000

44000-66000

22000-440000-22000

ApplicationsElement Mapping in Forensics

Section of a bullet• Distribution of

Fe, Cu, Pb, Ba

39,80 39,60 39,40 39,20 39,00 38,80 38,60 38,40 38,20 38,00

33,62

33,42

33,22

33,02

32,82

32,62

32,42

32,22

32,02

31,82

135000-150000

120000-135000105000-120000

90000-105000

75000-9000060000-75000

45000-60000

30000-45000

15000-300000-15000

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39,80 39,60 39,40 39,20 39,00 38,80 38,60 38,40 38,20 38,00

33,62

33,42

33,22

33,02

32,82

32,62

32,42

32,22

32,02

31,82

135000-150000

120000-135000105000-120000

90000-105000

75000-9000060000-75000

45000-60000

30000-45000

15000-300000-15000

ApplicationsElement Mapping in Forensics

Section of a bullet• Distribution of

Fe, Cu, Pb, Ba

39,80 39,60 39,40 39,20 39,00 38,80 38,60 38,40 38,20 38,00

33,62

33,42

33,22

33,02

32,82

32,62

32,42

32,22

32,02

31,82

32400-36000

28800-32400

25200-28800

21600-25200

18000-21600

14400-18000

10800-14400

7200-10800

3600-7200

0-3600

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39,80 39,60 39,40 39,20 39,00 38,80 38,60 38,40 38,20 38,00

33,62

33,42

33,22

33,02

32,82

32,62

32,42

32,22

32,02

31,82

32400-36000

28800-32400

25200-28800

21600-25200

18000-21600

14400-18000

10800-14400

7200-10800

3600-7200

0-3600

ApplicationsElement Mapping in Forensics

Section of a bullet• Distribution of

Fe, Cu, Pb, Ba

39,80 39,60 39,40 39,20 39,00 38,80 38,60 38,40 38,20 38,00

33,62

33,42

33,22

33,02

32,82

32,62

32,42

32,22

32,02

31,82

12600-14000

11200-12600

9800-112008400-98007000-8400

5600-7000

4200-56002800-4200

1400-2800

0-1400

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ApplicationsElement Mapping in Industry

Polymer mould with metal structures

• Area 2.9 x 2.9 mm• Meas. points 900• Meas. time 5 s• Total time 5 h 10 min

5 10 15- keV -

0

100

200

300

400

Pulses

Ca Ti Fe Cr Cu Sr Mo

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ApplicationsElement Mapping in Industry

Polymer mould with metal structures

• Distribution of Cr and Ca

41,1

0

40,9

0

40,7

0

40,5

0

40,3

0

40,1

0

39,9

0

39,7

0

39,5

0

39,3

0

39,1

0

38,9

0

38,7

0

38,5

0

38,3

0

31,94

31,54

31,14

30,74

30,34

29,94

29,54

29,14

8900-92008600-89008300-86008000-83007700-80007400-77007100-74006800-71006500-68006200-6500

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ApplicationsElement Mapping in Industry

Polymer mould with metal structures

• Distribution of Cr and Ca

41,1

0

40,9

0

40,7

0

40,5

0

40,3

0

40,1

0

39,9

0

39,7

0

39,5

0

39,3

0

39,1

0

38,9

0

38,7

0

38,5

0

38,3

0

31,94

31,54

31,14

30,74

30,34

29,94

29,54

29,14

8900-92008600-89008300-86008000-83007700-80007400-77007100-74006800-71006500-68006200-6500

41,1

0

40,9

0

40,7

0

40,5

0

40,3

0

40,1

0

39,9

0

39,7

0

39,5

0

39,3

0

39,1

0

38,9

0

38,7

0

38,5

0

38,3

0

31,94

31,54

31,14

30,74

30,34

29,94

29,54

29,14

6540-68006280-65406020-62805760-60205500-57605240-55004980-52404720-49804460-47204200-4460

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Summary and Outlook

The µXRF Spectrometer ARTAX features a fast multi-element mapping in the mm range for industrial and forensic samples

The fast exchange of the excitation source (X-ray tube, collimator, polycap lens) allows optimization of spatial resolution and detection limits

Bruker AXS continuous its development in the field of µXRF spectrometry

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Thank you for attending!

Please type any questions you may have in the Q&A panel to the right of

your screen and click Send.

Copies of this presentation and related microanalysis resource

materials will be emailed to you.

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