香港科技大学 - synl.ac.cn Sheny… · Spontaneous shape memory effect in single crystals...
Transcript of 香港科技大学 - synl.ac.cn Sheny… · Spontaneous shape memory effect in single crystals...
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香港科技大学Hong Kong University of Science and Technology
(HKUST)
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Magnetic and transport properties in the field-induced phase
transitions in Ni50Mn50-xInx Heusler alloys
Zhang XixiangPhysics, Hong Kong University of Science and Technology
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Introduction
The search for ferromagnetic materials suitable for application in semiconductor spintronics devices.
To allow efficient spin injection into the semiconductor, these materials must satisfy at least the following
1) Curie temperature significantly higher than the room temperature, the working temperature of semiconductors used industrially.
2) A very high spin polarization of the electron states at the Fermi level.
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Heusler alloys were predicted to be Half-metals
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Half metalkey material candidate for spintronics
%100==↓↑
↓↑
+−
nnnnonpolarizati
↑n ↓nand are electron density
↑n ↓nOr =0
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Nonmagnetic vs. Magnetic Materials
N(E)
E
EF
N(E)
E
Nonmagnetic Magnetic
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Half metals
EF
N(E)
E
Spins of all the conducting electrons pint to the same direction “Up”
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Heusler alloys of Higher-spin-polarization(much higher than the conventional ferromagnetic metals)
• spin polarization of the Co2MnSi Heuslercompound has been estimated to be 61% at 10 K.
(Kammerer et al. APL85, 79,(2004))
• Point-contact Andreev reflection measurements of the spin polarization yield polarization values for Co2MnSi and NiMnSb of 56% and 45%, respectively (L. Ritchie et al., Phys. Rev. 68, 104430(2003)).
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Polarization of Ferromagnetic materials
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Ferromagnetic shape memory alloys
Ferromagnetic Heusler alloys are well known ferromagnetic shape memory alloys– Martensitic transformation– Magnetic field induced strain – Applications in actuators – ….
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Typical Heusler alloys -Ni2MnGa
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Characteristics
275 280 285 290 295 300 305
-12000-10000-8000-6000-4000-2000
0200040006000
c
b
a
Stra
in(p
pm)
T(K)
Spontaneous shape memory effect in single crystals
Spontaneous shape memory effect in single crystals
Thermal-elastic martensitic transformation Shape memory effect
-20 -15 -10 -5 0 5 10 15 200.0
0.2
0.4
0.6
0.8
1.0
1.2
1.4
0.0
0.2
0.4
0.6
0.8
1.0
1.2
1.4
T=250 K
T=270 K
T=275 K
T=280 K
T=285 K
MFI
S (%
)
Magnetic field (kOe)
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H=0 H≥HA
Mechanism of field induced strain
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Characteristics of Ni2MnGa
• High temperature phase (or austenite) : ferromagnetic, low magnetic anisotropy cubic lattice
• Low temperature phase (martensite):ferromagnetic, strong magnetic anisotropy, tetragonal lattice
• Both phase are ferromagnetic metals
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Transition temperature shifts very slightly
M(T) curves with different applied magnetic fieldsF. Zuo et al PRB58,11127(1998)
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Temperature depedennt reistivityTemperature-dependent resistivity
Zuo et al, J. Phys.: Condens. Matter 11 (1999) 2821–2830.)
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CoNiGa alloys
0 100 200 3000.0012
0.0016
0.0020
250 260 270
1.65
1.70
Res
ista
nce
(mΩ
)
Temperature (K)
Co5Ni2Ga3
R
esis
tanc
e (Ω
)
Temperature (K)
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0 50 100 150 200 250 300
0.5
1.0
1.5
2.0
2.5
-60 -40 -20 0 20 40 60
1.54
1.55
1.56
1.57
T = 250 K
ρ (m
Ω)
H (kOe)
Co5Ni2Ga3H = 50 kOe
MR
(%)
T (K)
Magnetoresistance
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Ni2MnCoIn crystalsNature 439, 957(2006)
MBErr
•−=
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Ni50Mn50-xInx single crystals(x=14-16.3)
• single crystals were grown at a rate of 5–30 mm/h using a Czochralski instrument with a cold crucible system
• X-ray: High temperature phase is L21-type ordered structure with a lattice constant a=6.006Å.
• Cooling to 93K, the crystal structure changes to an orthorhombic structure with a rather complex martensitic modulated sub-structure.
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Magnetic, electrical and thermal transport measurements
• Magnetic measurements: Quantum Design SQUID magnetometer, 2-400 K, 5 Tesla
• Transport measurements: Quantum Design Physical Property Measurement system (PPMS), 2-400 K, 9Tesls
• Specific Heat: PPMS
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0
20
40
60
80
100
120
140
0 40 80 120 160 200 240 280 320 360
0.4
0.8
1.2
1.6
2.0
2.4
a
c
d
a
b
T (K)
ρ (μΩ
.m)
x10
H (T) 0.01 3.0 5.0 7.0
M (e
mu/
g)
bTC
d
c
b
a
H (T) 0.0 3.0 5.0 7.0
M(T) and ρ(T) in different fields
Features:
(1) The martensitic transformation with thermal hysteresis.
(2) Martensitic transformation is magnetic field dependent.
(3) Magnetic field shift transition to lower temperature.
(4) The transformation can be totally suppressed by magnetic field.
(5) Currie temperature Tc=315K
(6) Low-T martensite is ferrimagnetic, poor metal.
(7) High T, ferromagnetic austenite, metal
(8) Martensitic transformation is accompanied by a metal-poor metal transition.
GMR in a broad temperature range
(APL91,2007)
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0 50 100 150 200 250 300 350 4000
20
40
60
80
100
-Δρ/ρ(
0)
T (K)
At 5K, for Crystal 1 MR =86%
GMR in a broad temperature range
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Giant MR and Tunneling MR
H
ρ
ρΤ ρ||
Giant MR (GMR) ρΤ = ρ||
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-120
-80
-40
0
40
80
120
-10 -8 -6 -4 -2 0 2 4 6 8 10-80
-60
-40
-20
0
0 3 6 935
40
a
H (T)
MR
(%)
M (e
mu/
g)
b
20 K 70 K 90 K 170K
20 K
M(H) and MR(H) in different fields
M(H) curves indicate a metamagneticbehavior or field-induced phase transition
ρ(H) or MR (H) has the similar transition fields
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Superzone GapSuperzone gap: The antiferromagnetic lattice does not
commensurate with the crystal lattice, which leads to a new Brillouin boundary
(a gap appearing on the Fermi surface).
• In intermetallic alloys, the large MR results from the collapsing of the “superzone gap” due to field induced first order phase transition. (UNiGa, PRL77,5253).
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0 50 100 150 200 250 300 3500
5
10
15
0
50
100
150
0.0
0.5
1.0
1.4
1.9
T (K)
c
3 T
0 T
a
0.01 T
3 T x12
M (e
mu/
g)
b
κ (w
/K.m
)
3 T
0 T
ρ (μΩ
.m)
Ni50Mn33.7In16.3 single crystal
Showing the similar martensitictransformation, metal-poor metal transition, GMR and Giant Thermalconductivity.
Free electron Wiedemann-Franz law
281045.2 −− Ω== KWxLTkσ
the upper bound for Δκel
The sum of Δκel and zero-field κgives total κ
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0.0 2.0 4.0 6.0 8.00
20406080
100
-60
-40
-20
0
H (T)
T=60 K
Δκ/κ
(%)
Δρ/ρ
(%)
M(H) and MTC(H) in different fields
The largest magneto-thermal conductivity
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0 50 100 150 200 250 300 3500
20
40
60
80
100
120 -Δρ/ρ(0) Crystal 1 -Δρ/ρ(0) Crystal 2 -Δk/k(0) Crystal 2
-Δρ/ρ(
0) &
Δk/
k(0)
(%)
T (K)
At 5K, for Crystal 1 MR =86%
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Specific heat measurement
0 50 100 150 200 250 300 350 4000
100
200
300
400
500
600
Curie temperature
Martensitic transition
0 T 9 T
C p (μJ
/K.m
g)
T (K)
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Specific heat measurement
0 200 400
0.2
0.4
0.6γ9T=0.076(mJ/g.K2)
γ0=0.039(mJ/g.K2)
T2 (K2)
C P/T (μ
J/K2 .m
g)
CP=γT+AT3 ( ) ( ) 3/1*23/191 nmV Bk
m hπγ =
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MR obtained from Specific Heat measurement
3/1)(0
90
9n
n TT =γγ 4.7
09 ≈n
n T
090 ]./1/1[)0(/)]9()0([ nnnTMR T−=−= ρρρ
τρ 2nem=
MR =86.4%
Excellent agreement
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Conclusion
Large magnetoresistance (MR) and magnetothermal conductivity are due to the collapse of Superzone gap, when the magnetic field induced ferrimagnetic to the ferromagnetic phase transformation happens
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A combined giant inverse and normal magnetocaloric effect for
room-temperature magnetic cooling
(PRB76,2007)
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Magnetocaloric effect (MCE)H, T2Spin ordered
H=0, T1Spin disordered
H
dHT
THMTHSTHSSH
HHMMM ∫ ∂
∂=−=Δ
2
1
)),((),(),( 12
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Ferromagnet
TC
M
agne
tizat
ion
Temperature (K)
Only near the TC, dM/dT is large, leads to a significant MCERoom temperature application: GdGeSi , LAFeSi alloys
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Ni50Mn33.13In13.90 single crystal
0 50 100 150 200 250 300 350 4000
20
40
60
80
0 100 200 300 400
0500
10001500200025003000
9 T
5 T
1 T
T (K)
C (J
kg-1K-1
)
M (e
mug
-1)
T (K)
Martensite, Ferrimagnet with Tc = 183 KAustenite , Ferromagnet with Tc = 315 K
Tp=310K
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Metamagnetism vs Phase-transition
0.0 2.0 4.0 6.0 8.0 10.0
0
10
20
30
40
50
60
70
80
0.0 5.0 10.00
204060
312.5
307.5 302.5 297.5
295
292.5
290
M (e
mug
-1)
H (T)
310 315 320 325
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Calculation of entropy change
)1(1
1∑ Δ+−
−+=Δ−
i iHiMiMiTiT
SM
consantSM
H=
ΔΔ
=ΔΔθ
Clausius-Clapeyron equation
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Entropy change vs temperature
290 300 310 320 330 340-35
-30
-25
-20
-15
-10
-5
0
5
10
15
C-C equation
2 T 3T 4T 5T 6T 7T 8T 9T
9T
2T
a
-ΔS
(JK
g-1K-1
)
T (K)
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Loading
Heat exchanger
H
Cooling water Cooling water
Valve
Tube Loading
Heat exchanger
H
Cooling water Cooling water
Loading
Heat exchanger
H
Cooling water Cooling water
Valve
Tube
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Acknowledgement
• Collaborators:• Bei Zhang, HKUST• Guangheng Wu, Institute of Physics, Beijing• Jinglan Chen, Institute of Physics, Beijing• Shuyun Yu Institute of Physics, Beijing• ….
Financial supports 1) Hong Kong RGC 2) National Natural Science Foundation of China
(50571113)