EDS Analysis UsingUltra–Low Beam Currents · •Sum spectra of the three phases can be generated and phase ratio can be calculated. Phase . Area / pix: ... 7 cps/eV S Pb . Lead

Innovation with Integrity

Max Patzschke, Andi Kaeppel

Bruker Nano GmbH

EDS Analysis Using Ultra–Low Beam Currents

• Multiple element SDDs

• XFlash® 5060FQ

• Examples of fast/large area SEM/T-SEM-EDS using the FQ

Presenters

Max Patzschke

Application Scientist,Bruker Nano Analytics, Berlin, Germany

Andi Kaeppel

Product Manager EDS/SEM, Bruker Nano Analytics, Berlin, Germany

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• Introducing the X-Flash FlatQuad• Chip area vs. take of angle• Examples:• -high speed mapping• -large area maps• - samples without sample preparation• -samples with high topography • -Low kV analysis on sensitive samples and nano particles

Overview

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• Detector combines high count rate capabilities with high collection efficiency (solid angle)

• Application fields are:

• Particles or structures in nanometer range (low kV, smaller excitation volume)

• Beam sensitive samples (low probe current)

• Samples with high topography (avoids shadowing effects)

• Light element samples (low kV for ideal ionization cross-section)

• Thin (electron transparent) samplee.g. TEM/STEM samples (low x-ray yield)

• Ultra fast spectral mapping

• Large area mapping: mapping of neighboring areas and stitch maps together

XFlash® 5060FQ

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Four channel SDD: XFlash® 5060FQ

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Flat QUAD detector in combination with a conventional XFlashdetector at the Hitachi SU8000 series (Cold-Emission FE-SEM)

XFlash® 5060FQ

• 4x15mm²=60mm²

• capable of output count rates up to 4 x 400,000 cps= 1,600,000 cps

• annular design

• Central aperture for the primary beam

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Advantage of four elements Count rate capability

Output vs Input count rate, four channel SDD, 400kcps processors

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1800

1500

1200

900

600

300

0

OC

R /

kcps

0 750 1500 2250 3000 3750 4500ICR / kcps

OCR of up to 4 x 400,000 cps= 1,600,000 cps

Collection efficiency: solid Angle for X-ray collection

wikipedia

Ω = Asurf / r2 [sr]ΩEDS-SEM ~ 0.01 – 0.1 srare typical for side entry

ΩEDS-S/TEM ~ 0.1 – 0.4 srare typical for side entry

Some 100mm2 in STEM ~ 0.5srFEI Osiris 0.9 sr (4 x 30mm2)FEI ChemiSTEM 0.7sr (4 x )

Achieve higher solid angle by: Chip area A but, smaller areas have advantages:less cooling, less weight > higher stability, less pile up, better TOA >better P/B, better energy resolution, higher OCR/ICR = higher efficiency Distance d: get as close as possible

Ω =𝐴𝐴𝑑𝑑𝑑

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Advantage of large solid angle

max solid angle atd = 2.5mm:Ω > 1.1 sr

dΩ

Solid angle and OCR vs distance d

Nestor J. Zaluzec, Detector solid angle Formulas for Usein EDS, Microsc. Microanal., 15 (2009) 93

Cu, 1nA, 5kV

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XFlash® 5060FQ

dΩ

• Guaranteed energy resolution Mn-Ka 129 eV (other resolutions on request)

• 4x15mm²=60mm²

• annular design

• Central aperture for the primary beam

• designed to be placed between pole piece and sample

• Segments very close to sample

combination ofhigh count rate large solidcapability angle + high TOA

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Analysis of a capacitor

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Multilayer ceramic capacitor (MLCC): Layered structure of Si, Ti, Ni, Cu, Zr, Sn, Ba.

Acquired using Hitachi SU8040


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Conventional detector, Ω≈0.01sr

512x384pixels, HV=10kV, 170s, 260cps ICR, 41000 cts total


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Conventional detector, Ω≈0.01sr

512x384pixels, HV=10kV, 170s, 260cps ICR, 41000 cts total

XFlash® 5060FQ

512x384pixels, HV=10kV, 170s, 28kcps ICR, 4800000 cts total (same beam current)

Ω≈1sr> 100x


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XFlash® 5060FQ

512x384pixels, HV=10kV, 170s, 28kcps ICR, 4800000 cts total (same beam current)

Ω≈1sr


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• Analysis of single element distributions

Analysis of a capacitor:XFlash® 5060FQ

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• Identify significant phases andmark objects

• Use this information for a phaseanalysis: group similar specta (ignoringnoise), separate significantdifferencesPCA= principle component analysis


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• Investigate the sum spectra of the phases


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SnPlating

NiBarrier

CuTermination

BaTiO3dielectric

layer

• A lot of analysis methods can be applied to dataacquired in only 3 minutes!

Large area mapping with XFlash 5060F

Courtesy by Newsom, Univ. of New Mexico, Albuquerque

Mapping ofYaxcopoil-1 drillcore of Chicxulubimpact crater

20x19 imagesstitched together

7800x5500 pixel2µm per pixel19h total

acquisition time1.5 ms per pixel

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Courtesy by Newsom, Univ. of New Mexico, Albuquerque1 mmFe K Ca Mg Cl


20x19 imagesstitched together

7800x5500 pixel2µm per pixel19h total

acquisition time1.5 ms per pixel

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21Courtesy by Newsom, Univ. of New Mexico, Albuquerque


Zoom in interesting area and new map: andradite garnet (pink) in Mg rich matrix (purple)

1024x768 image0.4 µm per pixel

Fe K Ca Mg Cl 1 mm

φ=30..35°

Take-off angle comparison: XFlash® 5060FQ vs. conventional SDDs:

Advantage of high take-off angle andannular design

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φ=60..70°

Polymer composite containing organo clay

2 µm

XFlash 5060F QUAD + 5030 detectorPolymer compound

XFlash 5060F QUAD detector XFlash 5030

Courtesy by Dalto et al., Universidade Federal do Rio de Janeiro

3 kV, 220pA, 10 kcps, 320 s,1024x768 pixel

3 kV, 220pA, 0.8 kcps, 320 s,1024x768 pixelShadow effects due to rough surface

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Analysis of samples with high topography

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Sample containing C, Si, SiC

• Rough, broken-off surface, showing cracks and recess structures

• Difficult to analyze because of inclined surfaces

• Large absorption effects possible, especially for carbon

• Analyzed with Hitachi SU8040 cold cathode FE-SEM at HV=3kV


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Mapping of C, Si

512x384pixels, HV=3kV, 170s, 7.5kcps ICR, 1,200,000 cts total

Sample containing Si, SiC, C

• Mapping of carbon and silicon shows C rich (red), Si rich (blue, upper left) and Si-C containing phases


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Mapping of C, Si

512x384pixels, HV=3kV, 170s, 7.5kcps ICR, 1,200,000 cts total


• Application of an automatic phase analysis (combination of similar spectra) reveals more clearly the three different phases

• Almost independent of the topography


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• Sum spectra of the three phases can be generated and phase ratio can be calculated

Phase Area / pix Area / %C rich 117,000 60

Si rich 7,000 4

Si-C 72,000 36


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• Sum spectra of the three phases can be generated and phase ratio can be calculated

• Sum spectra can be quantitatively analyzed and indicate a C, Si and SiC phase

• Restrictions: C absorption effects due to inclined facets

Phase C / at.% Si / at.%C rich 98 2

Si rich 15 85

Si-C 45 55

Sample courtesy: L. Ferrière, Naturhistorisches Museum Wien

High vacuum analysis at low beam currentHistoric stony meteorite (“Mocs”)

XFlash® 5060F, Hitachi SU6600, 6 kV, <10 pA, 2 kcps, 47 min

• Fell 3rd February 1882 • Sample preparation

(coating) exluded• Lead contamination

(old polishing)• Pb-M and S-K can be

deconvolved using an online routine

1.80 2.00 2.20 2.40 2.60 2.80keV

0

1

2

3

4

5

6

7 cps/eV

S Pb

Lead deposition in cracks

Iron nickel sulfides

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XFlash® 5060F, Hitachi SU6600, 6 kV, <10 pA, 2 kcps, 15 h

1. Lead is deposited on top of silicates

2. Contamination withsoot by heating withcoal-fired furnaces


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<300 nm!

• Cultural heritage samples can be analyzed at the sub-µm scale without any sample preparation

• EDS at high vacuum offers better spatial resolution compared to low vacuum

XFlash® 5060F, Hitachi SU6600, 6 kV, <10 pA, 2 kcps, 15 h

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Low vacuum analysisParasitoid wasp (Monolexis fuscicornis)

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Head

In cooperation with: A. T. Kearsley & G. R. Broad (Natural History Museum, London)

• Low vacuum (20 Pa), 6kV, 240 sec, 800 x 600 pixel

• Tooth: Ca & P biomineralization of apatite Ca5(PO4)3(OH,F,Cl)


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• Low vacuum (20 Pa), 5kV, 30 min, 320 x 240 pixel

Ovipositor (sting and egg-layer)

Zn

O

Na

Cl


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• Low vacuum (20 Pa), 5kV, 30 min, 320 x 240 pixel

Ovipositor (sting and egg-layer)

0.80 0.90 1.00 1.10 1.20 1.30keV

0.0

0.5

1.0

1.5

2.0

2.5

cps/eV

Mg Na

Zn

Zn

O

Na

Cl

NASA Stardust mission: spacecraft collected samples of a comet and returned them to Earth

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• Test experiments necessary

• Micro crater generated by meteor like projectiles in Al foil

stardust.jpl.nasa.gov

25.07.2016 36

HyperMap: 3600x2700 pixel, 10keV, 1.0 Mcps ICR, 620 s,41 counts/pixel, reduced shadow effects

HyperMap / Spectral image / proof of principle exp.Micro crater generated by meteor like projectiles inAl foil, Hitachi SU6600 Schottky FE-SEM

Kearsley et al. 2011, Salge et al. 2011

25.07.2016 37

Analysis of a hole structure

25.07.2016 38

Magnified area: 480x360 pixel

TSEM-EDX of NPTypical Overview

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TSEM-EDX of fluorescent core shell NPSilica nanoparticles coated with Alexa® dye

XFlash FlatQUAD, 5 kV, 520 pA , 22.5 kcps, 250x250 pixel, 2 nm pixel size, 377 s

K. Natte, T. Behnke, G. Orts-Gil, C. Würth, J. F. Friedrich, W. Österle and U. Resch-Genger, J Nanopart Res, 2012, 14, 680

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TSEM-EDX of fluorescent core shell NPSilica nanoparticles coated with Alexa® dye

XFlash FlatQUAD, 5 kV, 520 pA , 22.5 kcps, 250x250 pixel, 2 nm pixel size, 377 s

Rades et al

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TSEM-EDX of NPClassification

„bulk“ NP „hollow“ NP

Hodoroaba et al

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0

10

20

30

40

50

60

0 50 100 150

Rel.

Inte

nsity

Distance/ nm

0

20

40

60

80

100

0 50 100 150

Rel.

Inte

nsity

Distance/ nm

0

5

10

15

20

25

0 50 100 150 200Re

l. In

tens

ity

Distance/ nm

„hollow“

„meso“„bulk“

In-lens TSEM

Si KαO K

• SiK / OK intensity ratio: independent of internal NP

morphology/structure• ! net local (inside NP) intensities

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„bulk“ NP

„hollow“ NP

unclassified NPSDD10 mm2

Flat QUAD

Acq time (s per NP) 120 2

ICR (kcps) 0.3 ≥20

Sol angle (sr) 0.01 1

NP identified 25 127

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Summary

• The XFlash® 5060FQ offers highest solid angle (1.1sr) + 4 x single throughput (1.600.000 cts) and collection angle of 60°– 70°

• allowing for

- Ultra fast mapping

- Nano particles

- large area mapping

- high topography no shadow effects

- Beam sensitive samples,

- SEM/T-SEM-EDS of

- bulk and

- electron transparent samples,

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GeozentrumNordbayernP. Schulte

Natural HistoryMuseum London

A. KearsleyG. Broad

Ocean Drilling Program

Federal Institute for Materials Research

and TestingD. Hodoroaba,

European Union

grant agreement n 263147… Risk assessmenst …

Institute of Meteoritics, University ofNew MexicoH. Newsom

Q&A

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Innovation with Integrity

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Documents

EDS Analysis UsingUltra–Low Beam Currents · •Sum spectra of the three phases can be generated and phase ratio can be calculated. Phase . Area / pix: ... 7 cps/eV S Pb . Lead