MANSE Midterm Review
II Materials
Chalcospinels
Delafossite oxides
Dilute oxide nanoparticles
Al-doped Co:ZnO thin films
Future work
MANSE Midterm Review
Staff, Publications
• M Venkatesan Senior postdoc
• Karsten Rode Postdoc
• Delphine Lebeugle Postdoc
• Jonathan Alaria Postgrad
• Marita O’Sullivan Postgrad
• Simone Alborgetti Postgrad
MANSE Midterm Review
Publications:
—Oxide dilute magnetic semicondutors – Fact or Fiction? J.M.D. Coey, S.A. Chambers, MRS Bulletin 33 1063-8 (2009)
—Dilute magnetic oxides and nitrides, K. Rode and J. M. D. Coey, in Handbook of Magnetism and Advanced Magnetic Materials (H Kronmullar and S Parkin, editors), Vol4, pp 2107 – 2121 (2007)
—Dilute magnetic oxides, J. M. D. Coey, Comments on Solid State and Materials Sciences 10 83-92 (2007)
—Magnetism in dilute magnetic oxide thin films based on SnO2, C. B. Fitzgerald, M. Venkatesan, L. S. Dorneles, R. Gunning, P. Stamenov, J. M. D. Coey, P. A. Stampe, R. J. Kennedy, E. C. Moreira and U. S. Sias, Physical Review B, 74, 115307 (2006)
— Giant moment and magnetic anisotropy in Co-doped ZnO films grown by pulse-injection metal organic chemical vapor deposition, A. Zukova, A. Teiserskis, S. van Dijken, Y. K. Gun’ko and V. Kazlauskiene, Applied Physics Letters, 89, 232503 (2006)
— Charge-transfer ferromagnetism in oxide nanoparticles, JMD Coey, KwanruthaiWongsaprom, J. Alaria and M. Venkatesan, Journal of Physics D: Applied Physics, 41, 134012 (2008)
— Magnetic, magnetotransport and optical properties of Al-doped Co-doped ZnO thin films M. Venkatesan, P. Stamenov, L. S. Dorneles, R. D. Gunning and J. M. D. Coey, Applied Physics Letters 90 242508 (2007)
—Magnetic and structural properties of Co-doped ZnO thin films, L.S. Dorneles, M. Venkatesan, R. Gunning, P. Stamenov. J. Alaria, M. Rooney, J.G. Lunney, J.M.D. Coey, Journal of Magnetism and Magnetic Materials 310 2087-2088 (2007)
MANSE Midterm Review
— Room temperature ferromagnetism in Mn- and Fe-doped indium tin oxide thin films, M. Venkatesan, R.D. Gunning, P. Stamenov, J.M.D. Coey, Journal of Applied Physics, 103, 07D135 (2008)
— Structural and magnetic properties of wurzite CoO thin films, J. Alaria, N. Cheval, K. Rode, M. Venkatesan and J.M.D. Coey, Journal of Physics D: Applied Physics, 41, 135004 (2008)
— Magnetism of ZnO nanoparticles doped with 3d cations prepared by a solvothermalMethod, J. Alaria, M.Venkatesan and J.M.D. Coey, Journal of Applied Physics 103 07D123 (2008)
—Magnetism’s ticklish giant, Nature Materials 5 677-8 (2006)
—Magnetic properties of CNx whiskers. R. D. Gunning, M. Venkatesan, D. H. Grayson and J. M. D. Coey, Carbon, 44 3213-7 (2006)
—The origin of Magnetism of etched silicon. P. Grace, M. Venkatesan, J. Alaria and J.M.D. Coey, Advanced Materials (in press)
—Absence of toroidal moments in aromagnetic anthracene. S. Alborghetti, E. Puppin, M. Brenna, E. Pinotti, P. Zanni, J.M.D. Coey, New Journal of Physics 10 063019 (2008)
—Thin films of semiconducting lithium ferrite produced by pulsed laser deposition, R.D. Gunning, Karsten Rode, Sumesh R.G. Sophin, M. Venkatesan, JMD Coey, Igor V. Shvets, Applied Surface Science (in press)
—Half-metallic Ferromagnets, M. Venkatesan, in Handbook of Magnetism and Advanced Magnetic Materials (H Kronmullar and S Parkin, editors), Vol 4, pp 2133 –2156 (2007)
MANSE Midterm Review
— Ferromagnetic nanoparticles with strong surface anisotropy: Spin structures and magnetisation processes, L. Berger, Y. Labaye, M. Tamine, J.M.D. Coey, Physical Review B 77 104431 (2008)
— Magnetic anisotropy of ilmenite-hematite solid solution thin films grown by pulsed laser ablation, K. Rode, R.D. Gunning, R.G.S. Sofin, M. Venkatesan, J.G. Lunney, J.M.D. Coey and I.V. Shvets, Journal of Magnetism and Magnetic Materials, 320, 3238 (2008)
—Permanent Magnets, T. Ni Mhiochain and J. M. D. Coey, Encyclopedia of Life Support Systems Volume 3: Physical methods, instruments andmeasurements, Y. M. Tsipenyuk (editor),.Chapter 10 pp 203 – 258 EOLSS/UNESCO Paris (2007)
MANSE Midterm Review
Characterization
• X-ray/Neutron diffraction
• SEM/EDAX/RBS/AFM/MFM/HRTEM
• SQUID magnetometry
• Optical spectrometry
• XAS/XES/XMCD
• Transport measurements
MANSE Midterm Review
I. Chalcospinels
Chalcospinels
Normal cubic spinel structure. n-type magnetic semiconductors
CuCr2S4 TC = 420 K 4.6 µB/f.uCuCr2Se4 TC = 460 K 4.9 µB/f.uCdCr2Se4 TC = 130 K
Conduction electrons may be fully spin polarized - potential half-metal?
A red shift (0.05 eV) of the absorption edge on passing the TC.High room temperature magneto-optical Kerr effect (1.2º at 0.9 eV).
MANSE Midterm Review
CuCr2Se4 ceramicPrepared at 550°C (below peritectic transition)
MANSE Midterm Review
High temperature synthesis
5.2850
5.5750
6.0550
σ (µB) @5KTemp (°C)
MANSE Midterm Review
PLD films
Deposition conditions
Ceramic target
Substrate c-Al2O3, MgO, MgAl2O4, RT-700°C
1 J/cm2 5Hz
Pressure ~ 10-6 mbar
Metallic target
Substrate MgO 200°C
1 J/cm2 5Hz
Pressure ~10-6 mbar
Annealing process
500°C in Se Vapour (from elemental Se powder) in a vacuum sealed quartz tube for 48 hours
Growth of CuCr2Se4 thin films from ceramic target
MANSE Midterm Review
Magnetizaton
Before Annealing After Annealing
Films from metallic target
Polycrystalline samples, mixed phases
MANSE Midterm Review
CuCr2Se4-xBrx
PowdersPowders• Synthesis temperature is critical.
• Saturation magnetic moment of 6 µB/mol can be achieved in CuCr2Se4 made at
550 C. It is probably a half-metal.
Single crystalsSingle crystals• Metallic (CuCr2Se4) or intrinsic semiconductor (CdCr2Se4) when undoped
• Anomalous Hall effect and AMR
Thin filmsThin films• ~ Single phase after annealing
MANSE Midterm Review
Next steps
Complete torque curvesComplete torque curves
LowLow--temperature heat capacitytemperature heat capacity
IR optical conductivity (with IR optical conductivity (with DimitriDimitri Basov, UCSD)Basov, UCSD)
Thermal conductivityThermal conductivity
Neutron diffraction (LLB April)Neutron diffraction (LLB April)
Andreev reflectionAndreev reflection
AC Squid AC Squid magnetometrymagnetometry; Sensitivity 3 10; Sensitivity 3 10--15 15 A mA m2 2 for for
dc fields < 1 T. dc fields < 1 T.
If the mobility permits, demonstrate an all-ferromagnetic transistor.
MANSE Midterm Review
II. Delafossite oxides
CuAlO2
CuCrO2:Ca,MgCuInO2:Mg,Sn
Carrier density and mobility are the major factors that require to be improved.
Cu-delafossite is still considered to be a potential p-type semiconductor for transparent electronics.
MANSE Midterm Review
CuCrO2
CuCrO2p-type transparent conducting oxide (TCO)
Delafossite structure: A1+B3+O2
Crystal system: Rhombohedral
Space group: R-3m
Lattice parameters: a = 2.9761(2) Å, c = 17.102(1) Å
Bandgap: 3.2 eV
Antiferromagnetic: TN = 25K
Mg-doped CuCrO2High conductivity for p-type TCO: 220 S/cm (5% Mg)Thermopower +153 µV/K at 300K50% transparent to visible light (250 nm thick film)
MANSE Midterm Review
0.1 1 10 100 1000
450
500
550
600
650
700
750
800
H2201CCO
H2301CCO
H2401CCO
H2501CCO
H2701CCO
H2801CCO
H2901CCO2
H2901CCO
H2801CCO2
Cu2OCuCrO2
CuO, CuCr2O4
Cu2OCuCrO2
CuCr2O4
Amorphous
Cu2OAmorphous
CuCrO2
T (
oC
)
PO
2
(µµµµbar)
10%
5%
2%
Undoped
Mg Doping
10 kΩ4021.565020H2103CCMO
600 kΩ3111.565020H1703CCMO
5 MΩ2021.065010H0502CCMO
∞6351.970010H2301CCO
Conductivity (2 probe)
Thickness (nm)
Rep Rate (Hz)
Fluence(J/cm2)
T (oC)P (μbar)
Growth Conditions
10 20 30 40 50 60 70 80 90 100 110 120
(003
)
(006
)
(101
) (009
) (001
2)
(202
) (001
8)
(003
)
(006
)
(009
)
(001
2)
(001
8)
(101
)
(202
)
(003
)
(006
)
(009
)
(001
2)
(001
8)
(101
)
(202
)
(003
)
(006
)
(009
)
(001
2)
(001
8)
(101
)
(202
)
Inte
nsity
(ar
b. u
nits
)
2θ (deg)
H2301C C O
Cu 2O
(22
0)
H0502C C M O
Cu 2O
(11
1)
H1703C C M O
Cu 2O
(11
1)
H2 103C C M O
10% Mg
5% Mg
2% Mg
Undoped
PLD films
MANSE Midterm Review
0 50 100 150 200 250 300
0.00
0.01
0.02
0.03
0.04
0.05
0.06
0 10 20 30 40 50 60 702.5
3.0
3.5
4.0
4.5
5.0
5.5
6.0
ρ (
Ωcm
)
T (K)
H2103CCMO
ln(σ
) (S
cm-1
)
1000/T (K-1)
10% Mg
20 25 30 35 40 45 50
1
10
100
1000
10000
100000
(006
) C
uCrO
2
(009
) C
uCrO
2
(101
) C
uCrO
2(0
02)
ZnO
Inte
nsity
(C
)2θ (deg)
H2611ZCO_6*
10% Mg-CuCrO2/0.1% Al-ZnO/(0001)/Al2O3
MANSE Midterm Review
Growth of highly-crystalline native p-type delafossite oxide films CuCrO2, CuAlO2
Good quality n-type Al:ZnO films are also grown by PLD (mobility ~ 20 cm2 V-1 s)
Next steps: Make all-oxide heterostructures; pn junctions and pnp stacks. Use sapphire shadow masks.
Summary
MANSE Midterm Review
III. Dilute oxide nanoparticles
Systematic investigation of the magnetic properties of LSTO,
undoped and with transition metal doping (substitution for Ti at the 1.5 or 2.0 % level) for dopants ranging from Sc to Ni.
Tokura et al, PRL 1988
spd-band metal.
0.5 electrons per formula
γ = 5 mJ mol-1K-2
properties depend on oxygen stoichiometry
LSTO nanoparticle system
MANSE Midterm Review
Polymerized complex method, using Ti isopropoxide and nitrate
precursors
Bulk ceramic samples of undoped LSTO, and LSTO with 2 % 57Fe
doping were made by mixing and firing the components at 1000 °C.
The pellet was placed in a ceramic boat and sintered at 1150 °C for 24 h in air or flowing argon.
The nominal purity of the starting materials was 99.99 % or better.
X-ray diffraction
SEM/EDAX
TEMSQUID magnetometry
Mössbauer spectrometry
Nanoparticle synthesis
MANSE Midterm Review
(La0.5Sr0.5)TiO3:Undoped
-5 -4 -3 -2 -1 0 1 2 3 4 5
-0.0010
-0.0008
-0.0006
-0.0004
-0.0002
0.0000
0.0002
0.0004
0.0006
0.0008
0.0010
Gel cap I
Gel cap II
18/09/07
300 KGel cap I 29.5 mg
Gel cap II 29.3 mg
Mom
ent (
10-3 A
m2 )
µ0H (T)
-4 -2 0 2 4
-0.0025
-0.0020
-0.0015
-0.0010
-0.0005
0.0000
0.0005
0.0010
0.0015
0.0020
0.0025 300 K
20 K
10 K
5 K
4 K
2 K
28/09/07
LSTO TCD 65.0 mg Gel cap: 29.0 mg
Mom
ent (
10-3 A
m2 )
µ0H (T)
Paramagnetism due to S = 1/2 defects in the LSTO particles
MANSE Midterm Review
Magnetization
-5 -4 -3 -2 -1 0 1 2 3 4 5-2.0
-1.5
-1.0
-0.5
0.0
0.5
1.0
1.5
2.0
Mom
ent (
10-6 A
m2 )
µoH (T)
LSTO nanoparticles LSTO bulk
Nanocrystalline χdia = -4.1 10-9 m3 kg-1
Ceramic χdia = -1.2 10-9 m3 kg-1
The ceramics show a diamagnetic susceptibility that is
smaller by a factor of three than that of the nanoparticles.
0 50 100 150 200 250 300-24
-20
-16
-12
-8
-4
0
Temperature (K)
Mom
ent (
10-8A
m2 )
Gel cap LSTO nanoparticles + Gel cap LSTO nanoparticles LSTO ceramic
MANSE Midterm Review
TM: LSTO
-4 -2 0 2 4
-0.3
-0.2
-0.1
0.0
0.1
0.2
0.3
300 K
200 K
100 K
50 K
4 K
Co2% LSTO 18.5 mgM
om
en
t (A
m2 kg
-1)
µ0H (T)
Sc Ti V Cr Mn Fe Co Ni0.0
0.5
1.0
1.5
2.0
2.5
3.0
3.5
4.0 Ferromagnetic Paramagnetic
Mag
netic
mom
ent
Transition metal
-4 -2 0 2 492
94
96
98
100
Tra
nsm
issi
on (
%)
Velocity (mm s-1)
-10 -8 -6 -4 -2 0 2 4 6 8 1095
96
97
98
99
100
Tra
nsm
issi
on (
%)
Velocity (mm s-1)
Raw Fit
Fe3+
Fe2+
Fe3+
FeFe:LSTO
Ceramic
Fe:LSTO
Nanocrystalline
Co:LSTO
2% Co
MANSE Midterm Review
The nanocrystalline samples doped with the late transitionelements Fe, Co and Ni behave differently.
In addition to a temperature-dependent, Curie-Weiss term in the susceptibility, they all show a nonlinear, ferromagnetic-like component in their magnetization curves
The samples doped with cations from Sc – Mn all exhibit linear magnetization curves and a Curie-Weiss susceptibility
LSTO summary
MANSE Midterm Review
Phys Rev B 2007 Many oxide nanoparticles exhibit a tiny magnetization < 0.1 A m2 kg-1
ZnO: 5% M = Sc - Cu
TM: ZnO nanoparticles
Solvo-/hydrothermal technique
MANSE Midterm Review
All the samples prepared in series A, except for TM=Ni, are diamagnetic or paramagneticas expected for the dilution of the TM in the ZnO matrix.
Characterization
MANSE Midterm Review
Mössbauer spectra
Sample B
70% of the iron is a similar +3 state. However, 30% of the iron appears in a magnetically order form, identified from the spectrum as magnetite and hematite.
Sample A
No magnetic ordering of the iron, Fe3+, with an isomer shift of 0.37 mm s-1 relative to α-Fe, and a quadrupole splitting of 0.46 mm s-1, as expected for substituted Fe3+ on tetrahedral site in ZnO.A
B
MANSE Midterm Review
5%Co-doped ZnO nanorods
Hydrothermal, Zn acetate, Co acetate, NaOH,
120°C for 12h
ZnO nanorods
MANSE Midterm Review
Summary
In two nanoparticle systems — ZnO;M and LSTO;M the TM dopants
are usually paramagnetic. Ferromagnetic moments only apperar in some sample when M = Fe, Co or Ni.
Where it was possible to analyse the iron phases specifically, using Mossbauer spectroscopy, evidence of a ferromagnetic secondary
phase (αFe or Fe3O4) was found.
It is likely that much or all of the ferromagnetism in these materials can be explained by ferromagnetic secondary phases.
The origin of the room temperature ferromagnetism in the Fe and Ni
doped ZnO prepared with a non-homogeneous precursor is explained
by the presence of a secondary phase magnetite and metallic Ni,
respectively.
The evidence indicates that room temperature ferromagnetism in these doped ZnO nanoparticles has an extrinsic origin.
MANSE Midterm Review
IV. Al-doped Co:ZnO films
Zn0.95Co0.05O + x at.% Al
x = 0.1, 0.2, 0.5, 0.7 and 1 at.% Al
-1.0 -0.5 0.0 0.5 1.0-15
-10
-5
0
5
10
15
m (
10-8
Am
2 )
µ0H (T)
Zn0.95Co0.05O 450°C 6 min. 10 Hz C-Al2O3
Zn0.95Co0.05O + 0.2% Al 450°C 6 min. 10 Hz C-Al2O3
0.0 0.2 0.4 0.6 0.8 1.0
0.0
0.2
0.4
0.6
0.8
1.0
1.2
R-cut
C-cut
Mo
me
nt (µ
B/C
o)
Al content (at.%)
MANSE Midterm Review
0 1 2 3 4 50
20
40
60
80
100
Tra
nsm
issio
n (
%)
Energy (eV)
0.0 % Al
0.1% Al
0.2% Al
0.5% Al
0.7% Al
1.0% Al Eg
0 20 40 60 80 1000.1
1
10
100
0
0.001
0.002
0.005
0.01
0.0 0.2 0.4 0.6 0.8 1.0
0.01
0.1
1
T = 100 K
Ca
rrie
r co
nce
ntr
atio
n n x
102
0,
cm
-3
Al nominal concentration, %
Ha
ll R
esis
tan
ce
RH,
Ω/T
Temperature T, K
Band gap widening
0.01 0.1 1 10
0.01
0.1
1
∆E
g (
eV
)
nHall
x 1020
(cm-3)
ZnCoAlO
γ = 0.66(5)
γ = 0.33
m* = 0.26(3) me 0 5 10 15 20 25 30 35 40
-1.4
-1.2
-1.0
-0.8
-0.6
-0.4
-0.2
0.0
(b)
(a)
0 90 180 270 36041.0
41.5
42.0
42.5
43.0
Resis
tance R
, k
Ω
Angle θ, deg
Co
nd
ucta
nce
co
eficie
nt
σ2, x 1
0-6 S
Temperature T, K
22 2/ 3(3 )
2 *g eE nm
π∆ =h
1 1 1* e hm m m
= +
MANSE Midterm Review
0 2 4 6 8 10 12 140.0
0.2
0.4
0.6
0.8
1.0
1.2
1.4
1.6
Co
ndu
cta
nce C
oeff
icie
nt
σ2, S
Magnetic Field µ0H, T
257ZCAl2 (1% Al)
T = 2 K
T = 5 K
T = 10 K
T = 20 K
T = 50 K
0 1 2 3 4 5 6 7 8 9 10 11 12 13 14-3.5
-3.0
-2.5
-2.0
-1.5
-1.0
-0.5
0.0
C
on
du
cta
nce
Co
eff
icie
nt
σ2, S
x 1
06
Magnetic Field µ0H, T
236ZCAl2 (0.2% Al)
T = 2 K
T = 5 K
T = 10 K
T = 20 K
T = 50 K
MANSE Midterm Review
0 50 100 150 200 250 3000
20
40
60
80
100
Data
Exponential Fit
Data: Temp_F
Model: ExpDec1
Chi^2/DoF = 2143.51872
R^2 = 0.98547
y0 3.3 ±2.6 mT
A1 85.7 ±3.8 mT
t1 19.5 ±2.9 K
Co
erc
ive
Fie
ld H
c, m
T
Temperature T, K
0.0 0.1 0.2 0.3 0.4 0.5 0.62.0x10
-8
3.0x10-8
4.0x10-8
5.0x10-8
6.0x10-8
7.0x10-8
8.0x10-8
9.0x10-8
1.0x10-7
Satu
ratin
g M
om
ent m
s, A
m2
Inverse Temperature 1/T, 1/K
Saturating Moment
Linear Fit of Temp_D
A = 3.5(3) 10-8 Am
2
B = 1.2(1) 10-7 Am
2K/5T
-5 -4 -3 -2 -1 0 1 2 3 4 5-1.0x10
-7
-5.0x10-8
0.0
5.0x10-8
1.0x10-7
ZnCoO: 214ZC502
1.8 K
2.0 K
3.0 K
4.0 K
5.0 K
10 K
20 K
50 K
100 K
200 K
300 K
Co
rre
cte
d M
ag
ne
tic M
om
en
t m
c, A
m2
Magnetic Field µ0H, T
-1.00 -0.75 -0.50 -0.25 0.00 0.25 0.50 0.75 1.00-2x10
-7
-1x10-7
-5x10-8
0
5x10-8
1x10-7
2x10-7
T = 1.8 K
T = 300 K
Mag
ne
tic M
om
ent m
, A
m2
Magnetic Field µ0H, T
MANSE Midterm Review
Larger moments for films on C-cut substrates compared to R-cut substrates.
Magnetic moment decreases with increasing Al content.
Conductivity is enhanced significantly in films with lowAl doping (0.1-0.2 %), maintaining the magnetic moment.
Band-gap shift (~ 0.5 eV), is observed with Al-doping.
Summary
MANSE Midterm Review
Symposium on dilute magnetic oxides
Detailed electronic structure calculations with theorists in TCD
- LDA and spin transport calculations - Stefano Sanvito’s group
- Electronic structure of oxides - Charles Patterson’s group
Dopants and defects control magnetic properties
- X-ray magnetic circular dichroism (ISRF, Grenoble)
- XAS and XES (Cormac McGuinness) - Transmission electron microscopy (Peter Nellist)
Collaboration
Collaboration within SFI
MANSE Midterm Review
Future work
ChalcogenidesDetailed characterization on chalcogenide systems (Neutron,
Andreev etc.) and synthesis of single crystals
Materials developed will continue to be exploited for applications in MANSE.
Delafossite oxidesMake all-oxide heterostructures; pn junctions and pnp stacks.
Dilute OxidesSearch for new and novel dilute magnetic oxides by suitable
cation doping.
Nanoparticle systemsUnderstanding of defects, interface magnetism and detailed
theoretical calculations.
Heusler alloysExploit high Curie temperature Heusler alloys Co2MnSi, Co2FeSi etc.
MANSE Midterm Review
Outline
Background
TiO2:Fe
Magnetic silicon
Graphite
Anthracene
MgO:N
Au nanoparticles
A model — Charge-transfer ferromagnetism