Epitaxial Electrodeposition of

Metal Oxide Thin Films and

Superlattices for Energy
Conversion and Storage

Jay A. Switzer, Elizabeth Kulp, Rakesh Gudavarthy,

and Guojun Mu

Department of Chemistry
Materials Research Center
Missouri University of Science & Technology
Rolla, MO 65409, USA
Email: jswitzer@mst.edu
 Outline
• Electrodeposition of ceramic films

• Tilted ZnO nanospears on Si(001) – photovoltaics

& solid-state lighting

• Superlattices based on Fe3O4 – sensors & RRAM

memory
– Defect-chemistry superlattices based on Fe3O4
– Zn-doped Fe3O4 superlattices

• Electrodeposition of nanostructured lithium battery

materials
 Electrodeposition of metal oxides

Deposition methods

I. Redox Change
3Fe2+ + 4H2O  Fe3O4 + 8H+ + 2e-
II. Base Generation: 2H2O + 2e-  H2 + 2OH-
Zn2+ + 2OH-  Zn(OH)2  ZnO + H2O
Ca2+ + HCO3- + OH-  CaCO3 + H2O

III. Acid Generation: 2H2O  O2 + 4H+ + 4e-

Zn(OH)42- + 2H+  ZnO + 3H2O
Cu(OH)42- + 2H+  CuO + 3H2O
Electrodeposited Epitaxial Oxide Films

ZnO on Au(110) AgO on Au(111)

Cu2O on InP(111) CuO on Au(100)

 Applications of ZnO films and nanowires

Huang et al. Science 292, 1897-1899 (2001). Dietl et al. Science 287, 1019-1022 (2000).

D. Andeen et al. Adv. Funct. Mat. 16,

Tsukazaki et al. Science 315, 1388-1391 (2007). 799-804 (2006).
 CBD of Epitaxial ZnO(203) on Si(100)
0.9
Relative conc.

2-
+
Zn(OH)

Zn(OH)4
-
Zn(OH)3
0.6

0.3 Zn
2+
Zn(OH)2

0.0
log [Solubility]

-1.5

-3.0 Zn(OH)2 *
ZnO
-4.5 X-ray 2θ scan
-6.0
6 8 10 12 14
pH
Speciation and solubility of Zn(II) at 70 oC

SEM image of ZnO nano-spears on Si(100) ZnO(002) pole figure

 Tilted ZnO Nanospears on Si(001)

Epitaxial relationships: ZnO(203)[010] // Si(100)[010], ZnO(203)[010] // Si(100)[001],

ZnO(203)[010] // Si(100)[010], and ZnO(203)[010] //Si(100)[001]
 Magnetite – Fe3O4 (a = 8.394 Ǻ)
Inverse spinel = B(AB)O4 Tetrahedral sites : Fe3+
Fe(III)↓Td [Fe(II)↑Fe(III)↑]OhO4

Fe(III) antiferromagnetically coupled

Net ferrimagnetism due to Fe(II)
100 % spin polarization at Fermi level
Curie temperature = 860K

Octahedral sites: Fe2+ + Fe3+

8.00 Angstroms
 Magnetite-Based Magnetoreception

Bacterial Magnetoreceptors

Homing Pigeon Magnetoreceptors

Johnsen and Lohmann Physics Today 61, 29-35 (2008).

 Spin-Dependent Transport
Magnetoresistance
Fe3O4 on Au(111)
Ag Ag
Parallel Spins wire wire
iin iout
Low Resin
Resistance
Fe3O4
H
Super Glue

Glass
Antiparallel Spins

High
Resistance

Tunnel Barrier
or
Nonmagnetic
Layer
 Schematic of a Superlattice

b
a
b
a
b b

a a

Substrate

Science 247, 444 (1990) Chemistry of Materials 9, 1670 (1997)

Science 258, 1918 (1992) Chemistry of Materials 14, 2750 (2002)
Science 264, 1505 (1994) Science, submitted (2009)
 Cathodic Deposition of Fe3O4

Solution: 0.043 M Fe2(SO4)3 hydrate

0.1 M triethanolamine (TEA)
2M NaOH

Temperature: 60 to 90oC

Potential: -1.0 to -1.2 V vs. Ag/AgCl

Proposed Mechanism:
Fe(TEA)3+ + e-  Fe2+ + TEA
Scan rate = 50 mV/s
2Fe(TEA)3+ + Fe2+ + 8OH-  Fe3O4 +
J. Mater. Res. 21, 293 (2006)
4H2O + 2TEA Science, submitted (2009)
Using Applied Potential to Control Stoichiometry

Measured iV curve Calculated surface concentrations

Zn conc. as function of potential Lattice parameters as function of potential

 Fe3O4 superlattices produced by pulsing
between -1.01 V and -1.05 V

Transient of a superlattice produced by pulsing

potential between -1.01 V (3 s) and -1.05 V (1 s)

 = λ (N+ - N-)/ (2 (sin θ+ - sin θ-))

•N+ and N- are satellite orders
•λ is the x-ray wavelength
•θ+ and θ- are the positions of the high angle and low angle
satellites on the 2θ scan.
X-ray Analysis of a Superlattice ( = 12.5 nm) on Au(111)

(444)
superlattice

(111)
Au

Rocking curves
X-ray 2 scan
superlattice

Au

(311) superlattice pole figure (311) azimuthal scans at 30o

Zn-Fe3O4 superlattices produced by pulsing
between -0.99 V and -1.05 V
FIB Cross Section of a ZnxFe3-xO4
Superlattice  = 78 nm
Magnetoresistance of Zinc Ferrite
Superlattice (12.2 nm) at 45 K

142

Magnetoresistance (%)
0
Resistance (k)

140
-2
138

-4
136

134 -6
-10 -8 -6 -4 -2 0 2 4 6 8 10
Magnetic Field (Tesla)
Resistive Switching in Zinc Ferrite
Superlattice (12.2 nm) at 77 K
Resistive Random Access Memory RRAM ?

100 mV/s scan rate 10 mA/s scan rate

 Electrodeposition of Nanostructured
NaMnO2 for Li Battery Cathodes
➢Electrodeposition of NaMnO2 from Mn(II)-TEA in strong base

➢NaMnO2 is a precursor to LiMnO2

➢Electrical continuity

➢Nanostructured material has high surface area

➢Potentially high capacity

➢Does not revert to LiMn2O4 spinel on cycling

➢Functions as supercapacitor
Electrodeposition of Nanostructured NaMnO2
for Li Battery Cathodes

CV in Mn-TEA solution SEM of electrodeposited NaMnO2

 Acknowledgements
Students/Postdocs
Elizabeth Kulp
Rakesh Gudavarthy
Eric Bohannan
Hiten Kothari
Steven Limmer
Shuji Nakanishi
Shaibal Sarkar
Niharika Burla
Guojun Mu

Financial Support
National Science Foundation
CHE-0437346 CHE-0243424
DMR-0504715 DMR-0076338
Department of Energy - DE-FG02-08ER46518