2D XRD Imaging by Projection-Type X-Ray Microscope

National Institute for Materials Science,Tsukuba, Japan

Kenji SAKURAI

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1. Introduction - What’s projection-type X-ray microscope?2. Examples for inhomogeneous/patterned specimens3. Application to stress imaging4. Application to combinatorial imaging5. Summary and future outlook

Why 2D Imaging for X-Ray Diffraction ?Because inhomogeneous system is usual for many sciences

Microstructure- phase transition- diffusion

identification of materials- mixed crystal - polymorphism

physical property- residual stress- heat transfer

poly-crystalline materials - ceramics- metals- organic crystals

Macrostructure- grain growth- preferred orientation- dendrite

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2θ

I

‘Average’ information ?

Inhomogeneous mixture Grain boundaries

Textures

Synchrotronwide beam

Sample

X-Ray CCD camera with a collimator

PC

How to Obtain 2D Real Space Images?- Scanning vs. Projection (Reflection) Types -

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Extremely quick(~100msec)

Scanning type Projection type

High-resolution(~100nm)

XY scan

Fluorescent X-raysDiffracted X-rays

detector

SampleSynchrotronµ beam

T WroblewskiXRD (1995) K.SakuraiXRF movie (2003)

d1

Inhomogeneous sample

Inte

nsity

XRD imaging

Normal XRD

Energy scan

CCD

SR

Monochromator

X-Ray Energy

E0 E1 E2 E3

d3

d2

Collimator

How Projection-type Microscope Works? Monochromator scan like EXAFS experiments

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2dn sinθBn= λn

En=12.3981/λn

CCD

dtrPrimary

X-rays

Sample

Collimator

X-ray image Resolution: Δ= r/t×d

How Projection-type Microscope Works? The experiment is just simple exposures without XY scan

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BL-16A1Photon Factory

2.0 1.5 1.00

20

40

60

80

1006 7 8 9 10 11 12 13 1415

2 2 2

3 1 12 2 02 1 12 0 0

Inte

nsity

d [A]

1 1 0

Energy [keV]

Cr K absorption edge

Examples of 2D XRD ImagingPatterned metallic Cr thin films

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6100 eV(XRF)1 sec x 30

5765 eV(XRD)1 sec x 5

8mm

8mm

2θ 64 degCamera- Sample 13 mm

1.2 1.3 1.4 1.5 1.6 1.7

0

5000

10000

15000

20000

25000

(2 2 0)(1 0 9)

(1 0 10)

(3 0 0)

(2 1 4)

(0 1 8)(1 2 2)

(1 1 6)

(0 2 4)

a-Al2O

3

Inte

nsi

ty[c

ps]

1.2 1.3 1.4 1.5 1.6 1.70

1000

2000

3000

(4 2 0)

(1 3 1)

(4 0 1)

(2 3 2)(3 3 1)

(1 1 4)

(1 4 0) (1 2 3)

(2 3 2) (2 3 1)

(2 2 2)

(2 3 0)

(1 1 3)(3 1 2)

(3 1 1)

(2 0 3)

(0 3 1)

(2 2 2)

(3 1 1)

(3 1 0)

(2 0 2)

HfO2

Inte

nsi

ty[c

ps]

1.2 1.3 1.4 1.5 1.6 1.70

5000

10000

15000

20000

(8 3 3)

(8 4 0)

(6 6 2)

(8 3 1)

(6 6 0)(6 5 3)

(8 2 2)(8 1 1)

(8 0 0)

(6 5 1)(6 4 2)(7 2 1)

(6 4 0)(5 4 3)

(4 4 4)(6 3 1)

(6 2 2)

(5 4 1)

(6 2 0)

(6 1 1)

OCT0411

Inte

nsi

ty[c

ps]

[ﾅ]

HfO2

Y2O3 Al2O3

monoclinic HfO2 (-401)Energy:6630eV(bragg angle: 45.31deg.)

Cubic Y2O3 (662)Energy:7160eV(bragg angle: 45.45deg.)

alpha-Al2O3 (300)Energy:6345eV(bragg angle: 45.39deg.)

Viewing Area 13mm ×13mmViewing Area 13mm ×13mm

2d (Å)

Examples of 2D XRD ImagingDifferent materials in the same view area

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1.2 1.3 1.4 1.50

5000

10000

0

5000

7 6.5 6Energy [keV]

Cubic

Inte

nsity

[Cps

]

d [A]

(3 1 2)

(0 3 3)

Monoclinic

(1 1 3)

(2 3 0)(3 2 0)

(0 2 3)

(2 3 1)

(4 0 1)(2 2 3)

(4 0 0)(1 1 4)(1 4 0)

(2 2 2)(4 0 0)

Cubic ZrO2 (400)6787eV(d=0.1285nm)

Monoclinic ZrO2 (140)6889eV(d=0.1266nm)

13m

m

Normal XRD

Exposure Time10 secExposure Time10 sec

XRD images13mm

Examples of 2D XRD ImagingMapping of different phases of ZrO2

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50 100 1500

50

100

Inte

nsity

θ/2θ [deg]

Rutile Anatase

Incident beam:4900eV

R R

A

Examples of 2D XRD ImagingMapping of different phases of TiO2

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2θ=76deg 2θ=84deg Viewing area8×8mm

rutile(210)

anatase(200)

I1(x,y)= A1CA (x,y) +B1CB (x,y)

I2 (x,y)= A2CA (x,y) +B2CB (x,y)

CA (x,y) = A1B2 −A2B1

I1B2− I2B1

CB (x,y) = A1B2 −A2B1

I2A1− I1A2

Examples of 2D XRD ImagingQuantitative imaging for peak overlapping cases

9/23In

tens

ity

X-ray EnergyE1 E2

A1

A2

B1

B2

(220) (311)

Viewing Area 8mm × 8mmViewing Area 8mm × 8mm

Exposure Time1 secExposure Time1 sec

Line-pattern parallel to R.D. The strongest reflection is (311).

X-ray

R.D.

1.7mm

d=2.338Å3751eV

Optical PhotoRD

RD

d=1.1690Å7504eV

d=1.221Å7140eV

Normal XRD

d=1.431Å6130eV

7175 eV6125eV

40 60 800

50

100

(222)

(311)

(220)

(200) (111)Inte

nsity

[×10

3 cps]

2θ[deg.]

Examples of 2D XRD ImagingOrientation dependence of aluminum sheet (0.1mm t)

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sin2Ψ

Application to Stress ImagingStress analysis has been done by conventional XRD

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ψ2

2θ

X-ray ψ1 ψ3

σxσx

2θ2θ

larger ψ →larger εd+ ε1d d+ ε2d d+ ε3d

Diff

ract

ion

Ang

le, 2

θ(d

eg.)

2d sin θ=λ

Strain Peak shift

)(sin)(

1 2ψε

νσ φψ

∂∂

+=

Ex)(sin1

212 σσψσνεφψ ++

+=

Ev

E x

θθε Δ−=Δ

= cotdd

MK

Ex

⋅=

⋅∂∂⋅

+−=

180sin)2(

cot)1(2 20

πψ

θθ

νσ φψ

E Young ‘s modulusν Possion’s ratioθ Bragg angleΨ Orientation

Stress Stress

Changing incidence angle

)(sin121

2 σσψσνεφψ +++

=Ev

E x

MK

E

Ex

′⋅′=∂∂

⋅+

=

∂

∂

+=

ψλ

λν

ψε

νσ φψ

20

2

sin1

1

)(sin)(

1

sin2ψ

λ/λ 0

Sample

X-rays

Application to Stress ImagingHow to extend the method to 2D imaging ?

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ψ

CCD

2θX-Rays

Monochromator

CCD

0

2sin λλ−Ψ plot

Sample is always fixed Energy scan instead of 2θ scanChanging 2θ instead of incidence angle for ψ

Sin2ψ – λ/λo plot instead of sin2ψ – 2θ plot

Conventional XRD pattern (Cu Kα)

Blocks(low carbon steel)

Welded parts

Application to Stress ImagingImaging of welded steel

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6128eV 6184eV6070eV

CCD

Sample

X-ray 90°

Exposure time:5sec/image

Application to Stress Imaging2D images for Fe(200) reflections at 90 deg

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steel block

Welded part

CCD

Sample

X-ray

CCD

Sample

X-ray

CCD

Sample

X-ray

ψ=45.0° ψ=52.5°ψ=39.0°

Application to Stress Imaging2D images for Fe(200) reflections for different ψ

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ψ=52.5°ψ=39.0°

ψ=45.0°

Application to Stress Imaging2D images of peak shift amount (X-ray wavelength)

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steel block

Welded part

Wavelength

Inte

nsity

Inte

nsity

Wavelength

Inte

nsity

Wavelength

sin2ψ

λ/λ 0

Slope values for each pixelStress image

tensile

compressive

Application to Stress ImagingFinally obtained stress image from sin2ψ – λ/λo plots

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ψ=52.5°

ψ=45.0°

ψ=39.0°

Strain images for different ψ

Application to Combinatorial ImagingEfficient analysis of arrayed samples on a single substrate

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composition, temperature, … etc.

Para

met

ers

Sample-1, Sample-2,

.

....

Single-rod fishing Net- fishing

Abs

orpt

ion

E1 E2 E3 E4

XAFS

EA EB EC ED

XR

D in

tens

ity XRD

α-Al2O3(300)Energy: 6345 eV

Cubic Y2O3 (662)Energy: 7160 eV

monoclinic HfO2(401)Energy: 6630 eV

-

13m

m

13mm

Y2O3

Al2O3

HfO2

Combinatorial libraryGraded ternary oxides sample prepared by pulsed laser deposition.A. Ahmet, Y.-Z. Yoo, K. Hasegawa, H. Koinuma, T. ChikyowAppl. Phys. A 79, 837–839 (2004).

Application to Combinatorial ImagingScreening of high-k oxide candidates

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Fe-K XRF image8mm

8mm

SQsubstrate

100 oC

200 oC

300 oC

400 oC

Synt

hesi

s tem

pera

ture

Not

exposed

100 oC30 m

in

200 oC30 m

in

350 oC30 m

in KeK-PF BL-16A1Incident X-ray energy : 7130 eV(above the Fe-absorption edge)Imaging time : 3 secPixels : 1000 x 1000

Application to Combinatorial ImagingXRF/XAFS imaging of CO2 absorbing LiFeO2

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Chemical absorption of CO2→2 LiFeO2 + CO2 Li2CO3 + γ-Fe2O3←

CO2

Bulk Nano particles

CO2 exposure

7110 7120 7130

XR

F In

tens

ity (n

orm

)

X-Ray Energy (eV)

CO2 exposure Not exposed 100oC x 30 min 200oC x 30 min 350oC x 30 min

CO2 exposure

absorption edge shift

100 oC

200 oC

300 oC

400 oC

Quick change at lower

temperatureSynthesis tempera-ture

Application to Combinatorial ImagingXRF/XAFS imaging of CO2 absorbing LiFeO2

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0.5eV-step x 60 pointsMeasuring time = 9 min !!

400oC

200oC

2D XRD imaging by projection-type X-ray microscope

Different phases

Different orientations

Summary1M pixel imaging for ~ cm2 area

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Energy-dispersive experiments with fixed geometryGlancing angle to the sample surface 1~3 degDiffraction angle (CCD camera position) 60~120 degClose distance between the sample and CCD device 0.5~15 mmCollimator plate inside the CCD camera 6 mrad

Imaging of inhomogeneous/patterned polycrystalline specimensdifference in materials, phases, orientations …

Application to stress imaging

Application to combinatorial imaging Combining with XRF/XAFS imaging

Scanning microscope Projection microscope(Non-Scanning)

Geometry for the sample Vertical arrangement (for most cases)

Horizontal arrangement

Necessity of focusing the primary beam

Absolutely necessary Desirable for vertical direction

Typical spatial resolution 0.05– 2µm 15– 100µm

Typical primary beam size 0.1– 2.0µm x 0.1– 2.0µm 8～12mm (H) x0.4mm(V)

Typical observation area 30–300µm x 30–300µm 8-12mm x 8-12mm

Ideal polarization in terms of S/B ratio

Horizontally linear Vertically linear

Typical pixel numbers ca. 100 x 100 More than 1000 x 1000

Typical measuring time for one image

3 – 24 h 0.03 – 3 sec

SummaryBoth scanning and projection-types are necessary

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Towards FutureProjection-type microscope can be widely used

American Chemical Society,

?

Stress analysis

Combinatorial screening

Chemical reactionFunctionally graded materials

Diffusion

composite materialsDeposition

Phase transitionRapid Diagnostics

Realtime Movie3D/4D Imaging

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Mitsubishi Electric Engineering

We use a synchrotron but combination with X-ray tube is also promising ..

Mari MIZUSAWA NIMS Stress imagingHiromi EBA NIMS Combinatorial imagingMasahiko Shoji NIMS Image processingHiroshi SAWA Photon Factory, KEK BL-16AYusuke WAKABAYASHI Photon Factory, KEK BL-16AYoshinori UCHIDA Photon Factory, KEK BL-16AAtsuo IIDA Photon Factory, KEK BL-4A“Active-Nano” supported by MEXT, Japan government Photon Factory S-type Program

ReferencesK.Sakurai, Spectrochimica Acta B54, 1497 (1999).K.Sakurai, Photon Factory Activity Report 2001 Part A, 33. K.Sakurai and H.Eba, Anal. Chem. 75, 355 (2003).M.Mizusawa and K.Sakurai, J. Synchrotron Rad. 11, 209 (2004).K.Sakurai and M.Mizusawa, AIP Conf. Proceedings (SRI-2003). (2004).K.Sakurai and M.Mizusawa, Nanotechnology, 15, S428 (2004).H.Eba and K.Sakurai, Materials Trans., 46, 665 (2005).H.Eba and K.Sakurai, Chemistry Letters, 34, 872 (2005).H.Eba and K.Sakurai, Appl. Surf. Sci., (in press).Japanese Patents1998-229180, 2002-138834, 2002-235592, 2002-235594, 2003-318922, 2005-066097, 2005-066120, 2005-114013

AcknowledgementThank you !

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Point AnalysisPoint Analysis

σ=K･M

M is the slope in 2θ-sin2ψ plotK=-32.44kg/mm2/deg

Stress

1

2

3

45

Measuring Point （No.1～5）

2D image analysisregion

2θ-sin2ψ plot

Optical microscope imageOptical microscope image

Incident X-rayEnergy 10.0 keVIncident X-rayEnergy 10.0 keV

Exposure Time1 sec.Exposure Time1 sec.

X-ray imageX-ray image

8 mm

8 mm

Quick X-Ray Fluorescence ImagingMetallic Cr thin film on glass substrate

KL

M

X-ray Fluorescence