2d xrd imaging by projection-type x-ray microscope 2005 pdf/28 ix/sakurai... · k.sakurai xrf movie...
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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
3/25
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)
10/23
sin2Ψ
Application to Stress ImagingStress analysis has been done by conventional XRD
11/25
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 ?
12/25
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
14/25
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)
16/25
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
18/25
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
24/25
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