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Single Crystal Neutron Diffraction. Single Crystal Neutron Diffraction. What What ‘‘s new?s new?
Arsen Gukasov, Laboratoire Léon Brillouin
CEA-CNRS, Saclay, France
Present state of SC Diffraction
Recent Applications of SC Diffraction
Polarized Neutron Diffraction
Spin density and local susceptibility
Polarization Analysis
Future Challenges
OUTLINEOUTLINE
Solids of Platon
waterearthfire air
5 Two-Dimensional Bravais Lattices
Hexagonal
Oblique Rectangular
Square
Two-Dimensional Bravais Lattices
a=b
Rectangular Rectangular Square Hexagonal
Two-Dimensional Bravais Lattices
a=b
Rectangular Rectangular Square Hexagonal
α=90° α=120°
Centered Bravais Lattices
a2
=0.5*arctng(1/2)* a1
a=b α=90°
Dmin
=0.5*Dmax
= a1
φ=arcsin(1/2)
Cmm
Cmm
P2
6mm
Two-Dimensional Space Groups
Cmm
P2
6mm
Square 2D Structures
P4 C4mm
14 3D Bravais Lattices
230 Space Groupes
Cannonball problem
The problem of close-packing of spheres was first mathematically analyzed by Thomas Harriot
around 1587,
after a question on piling cannonballs on ships was posed to him by Sir Walter Raleigh
on their expedition to America.
Cannonballs were usually piled in a rectangular or triangular wooden frame, forming a three-sided or four-sided pyramid. Both arrangements produce a face-centered cubic lattice –with different orientation to the ground.
FCC and HCP structures Density 0.74
Three-Dimensional Space Groups
2D Rectangular and 3D Orthorhombic Structures
P2mmPmmm
Tetragonal Rod Close Packings
The density is the same 0.7854.
P42
/mmcP4/mmm I41
/amd
Cubic Rod Close Packings
Density 0.5890
Pm3nI41
/amd
Density 0.6802
Rod Close Packings
P6/mmmThe density is 0.9069.
P4/mmmThe density is 0.7854.
FourierFourier
transform (transform (FTFT) and Diffraction pattern) and Diffraction pattern
s
=
FM (q)e-iqr
FourierFourier
transform (transform (FTFT) and Diffraction pattern) and Diffraction pattern
Lattice , and its FT :
Crystal 1 Molecule FT:
FT
of the crystal =Product of molecule FT and Rec. Latt. FT
Time of flight (TOF) neutron Diffraction from a single crystal
Multiple reflections sorted by Time-Of-Flight
SXD at ISIS, TOPAZ at SNS ESS Mag
Diffractometer
SINGLE COUNTER DIFFRACTIONSINGLE COUNTER DIFFRACTION
000
a*b*
-340
D
-140
sin(hkl )= /2Dhkl
0
50
10 0
150
2 0 0
2 50
3 0 0
-1.5° omega +1.5°
4-circles
4-
cercles : D9,D10, 6T2,5C2,TRICS(High resolution crystallography)
Bras levant : D3,D15, D23, 6T2, 5C1 (diffraction in extreme conditions)
First generation neutron diffractometers
UNPOLARISED NEUTRON DIFFRACTION UNPOLARISED NEUTRON DIFFRACTION 44--CIRCLESCIRCLES
Structure determination
Anharmonicity
Microcrystals
<0.05mm3 (PSD)
Epitaxial
layers(PSD)
DIFFRACTION USING PSDDIFFRACTION USING PSD
000
a*b*
-340
D
Diffraction conventionnelle:
-140
Diffraction using PSD :
Pre-project
Design
Realisation
Qualificatio n
Budget 380 k€ (50 kE Aquitaine R i )
33
• 256 position sensitive tubes(Ø ~ 1.2cm) 30b 3He efficiency 76% for 0.7Å �× 5height 47 cm �× 5•modular geometry:blocks of 16 paired tubes (2 tubes make one detector: less electronics and cables)
Opens to: 0.58Å measurements, more complex environments (HT), smaller samples, …
25
•
Berceau
équipé
de tables x,y,z•
Support X,Y,Z
•
λ
variables
( 2 Monok
avec foc
vert, 3 take- off)
•
Détecteur
2D
Take-off = 32° Take-off = 65°
S. GautrotV. KlosekM.H. Mathon
16 tubes L=100×2,54 cm P≈
12 bar
Conception (I. Goncharenko) : ~2004Construction : 2008-2009Operation started in march 2011
16 mars 2014 35
4f Magnetism and its Effects on Electronic Properties of Dy3
Ru4
Al12D.I. Gorbunov1,2*, M.S. Henriques3, A.V. Andreev1, A. Gukasov4, V. Petříček1, N.V. Baranov5, Y. Skourski6, V. Eigner1, M. Paukov2
4f Magnetism and its Effects on Electronic Properties of Dy3
Ru4
Al12D.I. Gorbunov1,2*, M.S. Henriques3, A.V. Andreev1, A. Gukasov4, V. Petříček1, N.V. Baranov5, Y. Skourski6, V. Eigner1, M. Paukov2
k=(1/2 0 1/2)
Minimum SC size for neutron studies?
a,b,c<10 A V>0.01mm3 (X-rays >0.0001mm3)
High resolution mode
1.36 m instead of 56 cm
•Pixels (2x2 mm) → résolution de 0.2°x0.2°
BiFeO3
, 0.7x0.7x4.10-2
mm3
CYCLOID WITH D=640 Ǻ
P [111]q1
Rotation plane : (-12-1) = P[111]
q1
Domain I
Domain IIP [1-11]
q1
Rotation plane : (121) = P’[1-11]
q1
P [111]
P [1-11]
q1
E
Neutron diffraction on thin films: what can we gain by using 2D detectors ?
20 22 24 26 281300
1400
1500
1600 1 0 +
Experiment Gaussian fit
1 0 -
Inte
nsity
(cou
nts/
60 s
ec)
(degrees)
(degrees)
2
(deg
rees
)
21 22 23 24 25 26 27 28
60
56
52
48
44
40
36100
120
140
160
180
(degrees)
2 (d
egre
es)
21 22 23 24 25 26 27 28
60
56
52
48
44
40
3620
40
60
80
100
120
Laplacian of Gaussian filtering
Cr 200 nm layer on Mg0
31,5 32,0 32,5 33,0
C r 0 0 2 rock ing sca n E xperim en t G auss ian fit
F W H M = 0 .23°
Inte
nsity
(u. a
rb.)
(degrees)
V=0.02mm3
UNPOLARISED NEUTRON DIFFRACTION UNPOLARISED NEUTRON DIFFRACTION NORMAL BEAM GEOMETRYNORMAL BEAM GEOMETRY
H, T phase diagramm
High pressure
photoexcitation
Diifuse
scattering (PSD)
6T2, Lifting counter mode
7.5 T + 40 mK
7.5 T +10 Gpa+40 mK
I.Mirebeau, I. N. Goncharenko, G. Dhalenne, A. Revcolevschi,Phys. Rev. Lett. 93, 187204 ( 2004).
Pi
=2.8 GPa; Pu
=0
Pi
=2.0 GPa; Pu
=0.3 GPa along 111
Pi
=2.4 GPa; Pu
=0.3 GPa along 011
T=0.14K
Tb2
Ti2
O7
a spin liquid single crystalunder pressure and applied field
Mapping of Spin ice
on the water ice
Oxygen
proton
If ferromagnetic
interactions, the ground configuration is «
two in –
two out
»
spins
Similar to ice ground state:«
two close –
two far
»
protons
with zero point entropy
Spin iceM.Harris, S Bramwell. Nature 399
(1999) 311 & A.P.Ramirez et al, Nature 399
(1999) 333
Cooling of Spin ice in field takes longer than without it
Double layered monopole structure in spin liquideA Sazonov, A Gukasov, I Mirebeau and P Bonville. Phys. Rev. B 85, 214420 (2012)
POLARIZED NEUTRON DIFFRACTIONPOLARIZED NEUTRON DIFFRACTION
M F HD
I+
I-
P0
parallel to H
P0
antiparallel
to H
R = I+ / I - = ( FN
+FM
) 2 / ( FN
- FM
) 2
R 1+4
FM
(q)=
FN
(q)
R = ( 1+ ) 2 / ( 1-
) 2, where = FM
/ FN
PND APPLICATIONSPND APPLICATIONS
Spin Densities
Magnetic structure refinement
Local Susceptibility Parameters (LSP)
Formfactors, L/S ratio
5C1 polarised neutron diffractometer (LLB)5C1 polarised neutron diffractometer (LLB)
monitor
samplecryomagnet 8T
lifting counter
magnetic guides
Heuslerpolarising
monochrom
ator
magnetic guides
cryoflipper
SPIN DENSITY OF SPIN DENSITY OF Mn(dca)2(pym)H2OMn(dca)2(pym)H2O
-1.00 0.00 1.00 2.00 3.00 4.00 5.00 6.00 7.00 8.00
-4.00
-3.00
-2.00
-1.00
0.00
1.00
2.00
3.00
4.00
5.00
�
� ��
� �
� �� �
�
��
�
M
n1
M
n2
N
7
C
8
C
5
C
7
H
1
C
6
H
2
O
1
N
8
0.00 1.00 2.00 3.00 4.00 5.00 6.00 7.00 8.00 9.00
-4.00
-3.00
-2.00
-1.00
0.00
1.00
2.00
3.00
4.00
5.00
N 4
N 5
N 6
C 3C
4M
nM
n�
�
��
�
�� �
�
��
�
pym=N2(CH)4 (pirimidine) dca=N(CN)2 (dicianamide)
Bulk magnetisation Mi (r)=ij j
NONNON--COLLINEAR SPIN DENSITIES COLLINEAR SPIN DENSITIES
H
Mz
HMz
H
Mz
Mx
I± F 2 N
±2(PP0 *FFM ) FN
+ FM
2
I± F 2 N
±2FMz FN
+ FM
2
F. Wang; A Gukasov et al., PRL, 2003 ORIGIN OF THE FIELD INDUCED METALIC STATE OF (La0.4
Pr0.6) 1.2
Sr1.8
Mn2
O
77
ANISOTROPIC SYSTEMS UNDER MAGNETIC FIELDANISOTROPIC SYSTEMS UNDER MAGNETIC FIELD
ANISOTROPIC SUSCEPTIBILITIESANISOTROPIC SUSCEPTIBILITIES
Bulk magnetisation Mi (r)=ij j
332322131211
ij
The number of independent components of ij is determined by the crystal symmetry class:
cubic groups 1 parameter all uniaxial
groups 2 parameters
Orthorhombic 3 ... Monoclinic 4 ... Triclinic 6
ANISOTROPIC SUSCEPTIBILITIESANISOTROPIC SUSCEPTIBILITIES
M
H
330001100011
ij
CUBIC, 11 = 22 = 33
M
H
110001100011
ij
ANISOTROPIC BULK SUSCEPTIBILITYANISOTROPIC BULK SUSCEPTIBILITY
UNIAXIAL 11 = 22 < 3
MMi
= a
aij
j
LOCAL SUSCEPTIBILITIESLOCAL SUSCEPTIBILITIES
I±
N 2 ±2FN
(PP0 *
aij
jj
) + |aij
jj
|2
I
N 2
2 P0z
N
Mz
+Mz2
R = I+ / I -, CHILSQ (CCSL)
A Gukasov
and P J Brown, J Phys C, 14, 8831, 2002
Magnetic monopoles
270 K 1 T, 100 FR
H // 111
MAGNETIC ELLIPSOIDS in TbTi
H II [111]
100 K 1 T, 100 FR
MAGNETIC ELLIPSOIDS in TbTi
H II [111]
50 K 1 T, 100 FR
MAGNETIC ELLIPSOIDS in TbTi
H II [111]
10 K 1 T, 150 FR
MAGNETIC ELLIPSOIDS in TbTi
H II [111]
5 K 1 T, 150 FR
MAGNETIC ELLIPSOIDS in TbTi
H II [111]
Ising
versus XYanisotropy
“as seen”
by PND. H. Cao, A. Gukasov
et al. PRL 103, 056402 (2009)
Can we measure ASPs on Powder samples?
powder Tb2Sn2O7 on Super-6T2, (measuring time 200 sec)
100k 5T
2k 5T
24°
Can we measure ASPs on Powder samples?
powder Tb2Sn2O7100k 5T
2k 5T
Can we measure ASPs on Powder samples?
CHILSQ program in CCSL (P J Brown)
Can we measure ASPs with upolarized neutrons?
Extinction rule for pyrochlore impose (00h)=4n
Im
(200)~χ12 Ising or XY behavior
Im
(400)~χ11 Heisenberg behavior
PND PROVIDESPND PROVIDES
Spin Densities
Magnetic structure refinement
Atomic Susceptibility Parameters
Non-collinear Magnetization Densities ?
Rectangular 2D Space GroupRectangular 2D Space Group
Pmm
Rectangular 2D Space Group Rectangular 2D Space Group PmmPmm
Pmm
Neutron beam
Laser
H
Optical Fiber
0P
crista l
PhotoPhoto--excitation setup at 5C1 diffractometerexcitation setup at 5C1 diffractometer
S. Decurtins et al. Inorg. Chem. 24 (1985) 2174
~ 514 nm
Light Induced Excited Spin State Trapping Light Induced Excited Spin State Trapping (LIESST) in (LIESST) in Fe(ptz)Fe(ptz)66
](BF](BF44
))22
0.00 2.00 4.00 6.00 8.00 10.00
4.00
2.00
0.00
2.00
4.00
6.00
8.00
0.00
2.00
-0.20-0.18-0.16-0.14-0.12-0.10-0.08-0.06-0.04-0.02-0.020.000.020.040.060.080.100.120.140.160.180.20
a
b
Very
Intense
Polarized Neutron DIFFRACTOMETER (5C1) at LLB
project started in 2006
+25 °
-5 °
M F
25°x90°
0.7 rad
VIP
Neutron DIFFRACTOMETER (5C1) deliverd in 2010
WISH diffractometer, ISIS TS2WISH diffractometer, ISIS TS2
85
• 256 position sensitive tubes(Ø ~ 1.2cm) 30b 3He efficiency 76% for 0.7Å �× 5height 47 cm �× 5•modular geometry:blocks of 16 paired tubes (2 tubes make one detector: less electronics and cables)
Opens to: 0.58Å measurements, more complex environments (HT), smaller samples, …
25
LAUE DIFFRACTOMETERS LAUE DIFFRACTOMETERS
Advantages:
Large angular covering (9 rad) High Luminosity, Small crystals Problems:
High Background, hkl overlapping,
Specrum Normalisation, Wavelength dependent corrections
SPIN DENSITY ON LIGANDS OSPIN DENSITY ON LIGANDS O22--
AND FORMFACTOR AND FORMFACTOR OF OF RuRu
in Sr2RuO4in Sr2RuO4
xy
t2g
A Gukasov, M Braden, R J Papoular, S Nakatsuji and Y Maeno PRL, 89, 087202-1, 2002
ANOMALOUS SPIN DENSITY ON OXYGEN IN Ca(Sr)ANOMALOUS SPIN DENSITY ON OXYGEN IN Ca(Sr)22
RuORuO44
Ru4+ 0.36(1)μB O2-
0.070(2)μB
19%
of Ru
Diffuse Scattering in Tb2
Ti2
O7
at 160mK
2D cuts in BZ with step δ= (0.25,-0.25,0) along the [1-10] axis
001
002
003
110
220
-1-10-2-20
2 0 0 3 1 0-0-2 0-1-3 0
001
002
003
160mK, H=0T 160mK, H=4T
Tb2Ti2O7 H II[1-10], [hhl] cut
160mK, H=1T
002
110-1-10
-1-10 110
002
00-2
111
Data Treatment (II)
Final peak extraction using Res. Parameters
Corrections (efficiency, Lorenz etc.)
I (hkl) , FR(hkl)
Evolution of Tb Anisotropy in TbMnOEvolution of Tb Anisotropy in TbMnO33
. .
200 K
150 K
100 K
75 K
Crystal Structure of LadderCrystal Structure of Ladder--Chain Compound SrChain Compound Sr1414
CuCu2424
OO4141
; ;
(h k l ) chain reflections
The = c1 /c2 =0.698(8)≈
0.7close to the commensurate value =7/10.
Sublattice
CuO2
a=11.4698, b=13.3527, c1
=2.7268 ( Amma)
( h k 0.7*l ) ladder
reflections
(hk0) common reflections of both
Sublattice
Sr2
Cu2
O3 a=11.4698, b=13.3527, c2
=3.9235 (Fmmm)
Reciprocal Reciprocal ––space viewspace view CuO2
Amma : k+l =2n
Sr2
Cu2
O3 Fmmm
: k, l=2n
Reciprocal Reciprocal ––space viewspace view CuO2
Amma : k+l =2n
Sr2
Cu2
O3 Fmmm
: k, l=2n
satellite (composite) reflections from interaction of lad-ch
Crystal Structure of LadderCrystal Structure of Ladder--Chain Compound SrChain Compound Sr1414
CuCu2424
OO4141
; ;
Crystal of cylindrical shape of about 4x3x2.5 mm3
~20 mm3
Measured reflections
1172, indep. 688., obs. (I ≥
3 s(I)) 502
hkl0 hk0m (hkl±1) (hkl±2)
R F2 6.25 3.11 11.86 36.66
*1c)(*b*a*
2c*1c*b*ahklmq mlkhmlkh
SrSr1414
CuCu2424
OO4141
, Super, Super--Space Group refinement Space Group refinement
J Etrillard, A Gukasov, M Braden. Physica C 403, 2004 and Phys Rev B 69, 214426, 2004