Fabrication and characterization of epitaxial

BiFeO3 - BaTiO3 nano scale hybrids using

nanosphere lithography

V. Rajasekarakumar, S. Bhattacharyya and Ram S. Katiyar

Department of Physics, University of Puerto Rico, San Juan PR 00931
 INTRODUCTION

Materials with coupled electric, magnetic, and structural order parameters are
called as biferroics.

Biferroic materials present opportunities for potential applications in

information storage, the emerging field of spintronics, and sensors.

Development of this new generation of materials have enriched significantly our

basic understanding of the underlying mechanisms of ferroelectricity and
ferromagnetism as well.

As the demand for higher device-density pushes the existing processing
techniques to their limits, ordered nanostructures become more welcome for the
futuristic multifunctional devices coupling these interesting properties at a
nanometer level.

. Self-assembled nanostructures have attracted particular attention in recent

years due to their potential applications in economic and versatile patterning of a
wide variety of materials at the nanometer scale with tunable array size and
density.
 PRESENT WORK

Fabrication of template layers using self-assembled array of polystyrene
spheres (PS) beads.

The monolayer formation of the template forming spheres on SrTiO3 was

verified using cross sectional SEM and AFM.

BiFeO3 –BaTiO3 thin films with a thickness range form 50 –100 nm were
deposited on these porous templates layers by pulsed laser deposition
technique.

The BiFeO3 –BaTiO3 nano-islands obtained from 460 nm diameter PS

templates were observed from SEM and AFM measurements.

X-ray diffraction studies showed the formation of crystalline and epitaxial

BFO-BT on both SrTiO3 and on SrRuO3/SrTiO3 heterostructures.

The feasibility to produce nanostructures with less than 50 nm lateral sizes

have been verified in laser ablated Pt using PS diameter of 100-200 nm.
 Fabrication of nanostructures
Si Substrate
Heated at 4000C for 1 hour
in O2 atmosphere

Si02 Substrate
Coating of PS
dispersed in water

PS beads on Substrate

Deposition of BFO-BT

Coating material on
PS template layer

PS beads removal by etching

Nano Pattern of
BFO-
BFO- BT
 The voids formed by
monolayer arrangement of
PS beads are triangular.

 Pattern formed had array

of triangular islands.
 CHALLENGES

 Obtaining continuous monolayer

of polystyrene was difficult

SEM micrograph of polystyrene on Si substrate

To get the nano pattern

by removing the polystyrene
and getting undisturbed
periodic pattern is crucial.
SEM micrograph of etched polystyrene on Si substrate
 Successful formation of monolayer

 Monolayer was obtained

by tailoring the processing
parameters.

SEM micrograph of polystyrene monolayer on

Si substrate

 Formation of Monolayer
was verified by the cross-
sectional SEM.
500 nm

Cross-
Cross-sectional SEM micrograph of polystyrene on Si substrate
 Coatings on monolayer of polystyrene

30 nm of platinum coated

on monolayer of polystyrene
(PS 100).

AFM of Platinum coated polystyrene

monolayer on SiO2 /Si substrate

3-D AFM of Platinum coated polystyrene monolayer

on SiO2 /Si substrate
Nano patterns of different Metals- Focus on size reduction

Nano pattern of Gold

 size of nano dots - 120 nm

 size of PS sphere - 460nm.

nano-islands of Au on SiO2 /Si substrate

AFM of nano-

Nano pattern of Platinum

 size of nano dots - 30 nm

 size of PS sphere - 100nm.
nano-islands of Platinum on SiO2 /Si substrate
AFM of nano-
 Nano patterns using different deposition techniques

The double image probably due to the variation

in the angle between the substrate normal and
the incoming flux during the deposition.

nano-patterns of Pt by PLD on SiO2 /Si substrate.

AFM of nano-

 DC sputtering gave good

quality nanopattern.
nano dot of the size 30 nm was
obtained
AFM of nano-
nano-patterns of Pt by DC sputtering
 Template of PS100nm . 2
on SiO /Si substrate.
 Nano patterns of BFO-BT ( BiFeO3 – BaTiO3)

 Template layer of PS-460nm on

SiO2/ Si substrate

PS- 460nm template on SiO2 /Si

AFM of PS-
substrate.
 BFO-BT nano dots of 120 nm size
obtained on SiO2/ Si substrate
 BFO-BT deposited by PLD
 Deposition pressure- 100 mT.

AFM of nano- BFO-BT on SiO2 /Si

nano-patterns of BFO-
substrate.
Nano patterns of BFO-BT ( BiFeO3 – BaTiO3) on STO

 BFO-BT nano patterns obtained

on STO substrate
 BFO-BT deposited by PLD
Deposition pressure- 100 mT.
 Efforts are underway to get the
clear and continuous patterns.

AFM of nano-
nano-patterns of BFO-
BFO-BT on STO
substrate.
 X-Ray Diffraction
RT+ A650 C
0 Substrate Temp: R.T
(012)
Deposition press: 100 mT
Intensity (a.u)

Annealing Temp : 650 0C_ 1hr

*
(104)

(024)

(018)
Annealing attmosphere: O2
*

20 25 30 35 40 45 50 55 60

BFO-BT (204)
STO (200)
0
2θ

BFO-BT (102)
RT+ 650 C

STO (100)
BFO-BT film on SiO2 / Si substrate
XRD of BFO-

Intensity (a.u)
BFO-BT/SRO/STO

BFO-BT/STO

SRO/STO

20 25 30 35 40 45 50 55 60
2θ

XRD of BFO-
BFO-BT film on STO, SRO/STO substrates
 XPS- Analysis

 XPS showed the presence of Bi,

Fe,O,Ba&Ti in the nano structure.

 Observed valency Fe 3+

XPS-
XPS-Spectra for the nanostructured BFO-
BFO-BT
on SiO2 / Si substrate

XPS-
XPS-Spectra for the nanostructured BFO-
BFO-BT on STO substrate
 CONCLUSION

Continous monolayer of polystyrene template layer have been optimised
successfully.

Nano patterns of different metal have been tried and successfully formed
the patterns of nanodots of platinum of 30 nm size using the PS- 100nm
template layer.

BFO-BT ( BiFeO3 – BaTiO3) nano patterns with the dot size of 120 nm
was obtained using PS-460nm template.

BFO-BT ( BiFeO3 – BaTiO3) nano patterns were formed in SiO2/ Si and
Strontium Titanate (STO) substrates.

Fabrication of nano structures with BiFeO3 –BaTiO3 was found to
depend on the thickness of the film and the choice of the substrates.

ACKNOWLEDGEMENTS
This work was supported by the project NCC#-1034.
The help of Mr. José Ortiz Morales and Esteban Fachini in SEM and XPS measurements is gratefully
acknowledged.