Title
Workshop at APS in 2007
High Pressure Research at SPring-8
●BL01B1
XAFS/DAC
●BL04B1
Large Volume Press
●BL02B1
Single Crystal Study
X-ray diffraction
●BL04B2
High Energy X-ray Diffraction
●BL08W
Compton Scattering
●BL09XU
NRIXS
●BL10XU Exclusive HP station
X-ray Diffraction using DAC
●BL43IR
Infra Red Spectroscopy
●BL40XU
XRD: Time Resolved Exp.
●BL39XU
X-ray Magnetic Circular Dichroism
●BL35XU
Inelastic scattering
●BL12XU,B2 (Taiwan)
NRIXS, XAFS
●BL14B1
X-ray Diffraction : LVP
●BL22XU
●BL11XU
X-ray Diffraction：DAC (LT, Single Crystal.)
NRIXS, Mössbauer spectroscopy
SPring-8
: LVP
High pressure experiments at SPring-8.
Large volume (multi-anvil) press : BL04B1, BL14B1, BL22XU
ED-XRD, radiographic imaging, ultra-sonic technique, etc.
Diamond anvil cell : BL10XU and others
AD-XRD with laser heating, a lot of SR technique
Keys for studying the deep Earth’s materials
~ experiments under multi-megabar condition
* increase pressure (temperature) limit
* high flux x-ray beam technique
Outline
・ BL10XU : high pressure x-ray diffraction station
(1) X-ray focusing optics : XRD under multi-megabar
(2) simultaneous measurement system of Brillouin spectroscopy
and XRD with LH.
・ New attractive measurement technique :
Energy-domain synchrotron radiation Mössbauer spectroscopy
using high-flux neV resolution x-ray beam.
XRD under highest pressure at BL10XU
Mo at 0.4 TPa : X-ray focusing optics
Focusing optics by using double lens system
Up-stream focusing lens : large aperture (beam condenser) & long focal distance
Glassy-Carbon CRLs
2nd lens : micro-beam & high flux density
ANKA, Germany
10 mm
GC lens
Experimental Hutch 1
Brillouin spectrometer
BL10XU Optics Hutch
Undulator
Experimental Hutch 2
High Pressure XRD
YLF
or
YAG
Cryostat
double crystal (diamond 111)
monochromator
(3)
X- CCD
IP
X- CCD
CR Lens
CO2 laser
heating
DSS
16m
DAC
2nd CRL
@30 keV
Be-CRL: 66
4D Slit: 100 μm x 100 μm
SU8-CRL: 8th
Collimator: A1φ15 μm
Vertical
@30 keV
Be-CRL: 66
4D Slit: 100 μm x 100 μm
SU8-CRL: 8th
Collimator: A1 φ15 μm
Horizontal
σ = 3.7(1) μm
FWHM = 7.3(2) μm
σ = 4.8(2) μm
FWHM = 9.5(3) μm
Intensity [arb.]
Intensity [arb.]
Focused x-ray beam profiles
7.3 μm
7 um
Beam profile : FWHM
~ 7 um (vertical)
~ 10 um (horizontal)
At sample (DAC) position
9.5 μm
10 um
(knife edge method)
Vertical
0
5
Horizontal
10
15
20
25
30
35
40
Vertical position [μm]
40
35
30
25
20
15
10
5
0
15 um
Horizontal position [μm]
XRD under 250 GPa
with 2nd lens
Example: Fe (250 GPa)
Effective intensity again
500 times (as the same exposure time)
X-ray divergence (angler resolution)
≒0.01deg. (100μm/55cm, 0.2mrad)
(the case of first lens only）
：0.003deg. (0.5mm/11m)
for multi-megabar high pressure (and multi-thousand Kelvin) experiments
with very good statistic and rapid XRD measurement
High pressure and high temperature
in-situ Brillouin spectroscopy
using infrared laser heating combined
with XRD at SPring-8
Motohiko Murakami
Okayama University
Yuki Asahara , Naohisa Hirao, Yasuo Ohishi
Japan Synchrotron Radiation Institute
Nagayoshi Sata
IFREE/AMSTEC
Kei Hirose
Tokyo Institute of Technology
Brillouin scattering & X-ray diffraction simultaneously measurement
existence of the sound velocity distribution
sound velocity
Vi = ⊿ωλ/2sin(θ/2),
i = s (transverse), p (longitudinal)
（in a symmetric scattering geometry）
shear modulus
G = ρVs2,
ρ（density from XRD）
adiabatic bulk modulus
elastic properties of minerals under Earth’
Earth’s interiors condition
Ks = ρVp2 – 4/3G
In order to interpret seismic observation in Earth’interior
and global seismological models.
New combined system
Performance, Sample/measurement condition
Specimen : multi crystal (powder, only transparent sample)
Pressure range : ~ 150GPa, DAC
Temperature : ~ 3500K, Laser Heating
Sound velocities measurement : Brillouin scattering spectroscopy
Sample density : x-ray diffraction (with pressure standard)
System components
Brillouin scattering : Fabry-Perot interferometer,
symmetric geometry
Laser Heating : CO2 laser (sample’s transparency.
Temperature is measured from spectroradiometric method)
X-ray diffraction : BL10XU x-ray (50keV) & x-ray CCD
(lattice parameters, pressure measurement, sample phase
monitor)
Combined system at BL10XU/SPring-8
The system consists of three components,
(1) Brillouin specrtometer
Fabre-Perro interferometer
DAC stage (XYZ)
heavy-duty linear translation stages
(2) X-ray diffraction system
X-CCD, Focused x-ray beam(50keV)
(3) Laser heating optics
CO2 laser, Spectroradiometric temperature
measurement system
Preliminary Results
Experiment (1)
Microscopic views of polycrystalline
MgO before laser heating (42 GPa) and
on laser heating (49 GPa, ~2300 K).
Brillouin scattering spectra of MgO
XRD of MgO
Experiment (2)
A
B
C
Microscopic views of H2O (a) before heating
(6 GPa) and (b) at melting temperature, (c),
(d) at 2200 K and during Brillouin
measurement.
Brillouin scattering spectra and XRD profiles of
H2O before heating (6 GPa) and at melting
temperature, at 2200 K and after quenching.
The resent developed energy-domain
synchrotron radiation
Mössbauer spectroscopy at SPring-8
Takaya Mitsui
Japan Atomic Energy Agency
Makoto Seto, Yasuhiro Kobayashi,
Satoshi Higashitaniguchi
Kyoto University, CREST
- High pressure applications
Naohisa Hirao, Yasuo Ohishi
Japan Synchrotron Radiation Institute
Energy-domain SR Mössbauer spectroscopy
Behavior of iron in deep Earth materials under high pressure
differentiation of the early Earth, subduction and upwelling in the mantle,
formation of the Earth's magnetic field
Mössbauer spectroscopy for studying deep Earth’s materials
one of powerful methods to study the electronic and magnetic structures
of iron and iron containing materials
- MS from conventional radioactive source
- MS from time spectrum by nuclear resonant scattering at SR
- Energy-domain synchrotron radiation Mössbauer spectroscopy
by collimated SR x-ray and neV high energy resolution technique
* Conventional Mössbauer spectra (NOT time spectra)
ED-SR-MS
* HighlyOscillation
collimated and intense photon flux
Oscillation
* Micron probes with X-ray focusing optics
> 1) Applicability to very small samples, such as ~10 micron,
at multimegabar pressures
> 2) Quick measurements (a few hours)
> 3) Low iron-containing materials
well collimated high flux
velocity
velocity
and high
energy resolution
x-ray
beam
* No limitation from the synchrotron operation modes
(bunch
mod
es)
57Co
neV resolution X-ray source
for
Mössbauer spectroscopy
Nuclear resonant filtering of
synchrotron radiation by pure
nuclear Bragg reflection of
57FeBO single crystal
3
*high collimated and neV
energy resolution x-ray beam
Ee1
SR
ΔE~meV
Transition energy
14.4 keV
Doppler energy shift of Mössbauer absorption
ΔE~meV
²E ~ neV
Energy
Natural line width
- 0.19 mm/s
E0: Resonant energy of a
nuclear analyzer crystal
Electronically forbidden and nuclear
allowed Bragg reflection of 57FeBO3 (333)
(pure nuclear Bragg reflection)
Eg
57FeBO
3
A single-line Mössbauer filtering technique
(iron borate)
single crystal
@~Néel temperature
in magnetic field
ΔE~neV
(nuclear Bragg reflection
≈ the natural width of the nuclear level)
Smirnov et al. (1997) Phys. Rev. B 55, 5811.
Mitsui et al. (2007) Jpn. J. Appl. Phys. 46, L821
Experimental arrangement for energy-domain SR
Mössbauer spectroscopy and DAC
Mössbauer spectrum of Fe2O3
under multi-magabar
HP phase (RT)
P ～ 7 GPa
Spin flip
0.9
The
suggests
this<technique
P ～results
52 GPa
> Tthat
Tm
m
is suitable for applications of high
Antiferromagnetic-paramagnetic
(Nasu, et al.,1986)
pressure
experiments
Phase
- Earthtransition
and Planetary Sciences –
Distorted corundum
type
(Rh2O3-II)
*Required
exposure
time
is 1 or 2 hours
(Pasternak,
al.,1999;
even if @et204
GPa Rozenberg et al., 2002)
*The
profiles
of spectrum
very good.
Metal-non
metal
transitionare
(Badro,
et al.,2002).
*Suitable for HP experiment source
P > 100 GPa
Room temperature SR Mössbauer spectra of 57Fe2O3
polycrystalline at different pressure conditions.
The solid lines are fits
with
Spin
flipLorenzian
at Pc lines.
Pasternak, et al. PRL (1999)
6
5
4
3
2
1
(a)
0.8
Relative Transmission
α−Fe2O3 (hematite :
corundum)
AP(0.1MPa) : paramagneticNéelTemp. : 955K
1
H=51.4T
QS= -0.2mm/s
1
0.9 (b)
0.8
H=51.1T
QS= 0.4mm/s
Normal
43 GPa
1
0.9 (c)
QS= 1.0mm/s
91 GPa
0.8
1
(d)
QS= 1.1mm/s
121 GPa
0.9
1
0.9 (e)
0.8
QS= 1.4mm/s
204 GPa
0.7
-10
-5
0
5
Velocity (mm/s)
Exposure time : 1 ~ 2 hrs.
10
Future Plan :
Mössbauer spectroscopy and XRD
simultaneous measurement
ΔE=2.5meV@14.4keV
hσ
V
E=14.4keV or 43.2keV
BL10XU
XCRL
② HRM
Si(511)xSi(975)
Si(111)xSi(111)
Slit
Slit
H
H
Mirror
BL11XU
Dia.(111)xDia.(111)
① PM
11550Oe
0Oe
NaI
NaI
DAC
DAC
V
③ NMC
57FeBO (333)@75.8
NMC
3
57FeBO (333)@
℃ 75.8
3
℃
SIngle-line ultra monochmatized beam
Summary
High-pressure researches for deep Earth’s materials
using DAC at SPring-8
BL10XU : fundamental but still upgraded
- for higher pressure (and higher temperature)
high flux x-ray beam
tandem XCRL focusing optics
accurate XRD experiment under multi-megabar
- Simultaneous measurement (XRD & Brillouin spectroscopy)
Resent developed spectroscopy technique at SPring-8
- Energy-domain SR Mössbauer spectroscopy
electronic and magnetic properties for iron containing materials
under deep Earth’s condition