Switchable Ferroelectric

Diode and
Photovoltaic Effect in
BiFeO
3

(Science, Vol 329, April 2009)

Jose Antonio Pea Garcia
Mart Gutierrez Latorre

Switchable Diode
Diode: Crystalline piece with a p-n junction connected
to two electrical terminals
Switchable Diode: the polarity of the diode can be
reproducibly switched by the reversion of the applied
electric field

Photovoltaic Effect

It is the creation of voltage or electric

current in a material upon to exposure to
light

Main properties of ferroelectrics

They switch the crystal structure at a certain temperature
High symmetry (non ferroelectric)
Reversible

Low symmetry (ferroelectric)

Low simmetry
polarization

generates

polar

directions,

hence

They maintain the polarization state in the absence of a

voltage and the possibility to reverse the polarization
direction by applying an electric field

Main properties of ferroelectrics

They show photocurrent when illuminated, but not like
semiconductors (and thats the point!)

Theres only photocurrent in the polarization direction,

the origin is still unclear, but it works

Photocurrent density is low, but it is proportional to the

length in the polarization so its ok

BiFeO

Perovskite type unit cell with

a=3.96 and =89.3

Rhomboedral structure (R3c)

Curie Temperature: 1100 K
Nel Temperature: 653 K
Room temperature Polarization along [111]
Optical gap: 2.2 eV
-phase is metastable in air

Absorption Visible light

Vaccum conditions

Three BiFeO3 Crystals are studied

One ferroelectric domain, same space disposition,
different thicknesses (70, 80 and 90m)
Samples

BFO thickness(m)/A(mm2)

Electrodes

BFO1

70/ 2x2

Au/ 0.6 mm*

BFO2

80/ 2.5x2.5

Au/ 1.6x1 mm2

BFO3

90/ 1x2

Au or Ag/ 0.6 mm*

*Diameter-circular thick

Samples
Au

Au
BFO

BFO

Au
BFO1

Au
BFO2
Ag
BFO
Ag
BFO3

Experiment 1
Sample: Au/BFO1/Au; Dark conditions

Au
BFO
Au
BFO1

First the diodelike behavior and temperature effect are

studied

Results
Diodelike behavior is observed
Current density increase with Temperature
Rectification ratio(R=J(E=+1.3)/J(E=-1.3) increase with
Temperature
Temperature (K)

Rectification ratio

200

13

250

159

300

488

350

495

Polarization switch does not occur

Ag

Experiment 2
The polarization direction clearly has relevance

100 Pulses= 150 V (E=17kV/cm)/ t= 0.01 s

PFM: 1Vrms and f=17 kHz

BFO
Ag
BFO3

Results
Flip in the electric polarization
after 150-V pulses
The diode forward and reverse
directions switch when the
direction of P is reverserd
The aplication of the second set of +150-V pulse does
not restore original configuration

Au

Experiment 3

BFO
Au

Sample: Au/BFO2/Au; Green light (=532 nm)

Then the photocurrent is studied

Au

BFO

Right

Au

Left

BFO2

Results
When a bias potential is applied to the material the
photocurrent follows the bias
When there is no bias, it follows the polarization direction,
and is always negative
Illumination-side

Photocurrent
(V=0), (A)

Reverse Vias
(A/cm2)

Left-side

-0.13

8.219

Right-side

-0.013

0.849

Left-side illumination works better than right-side

illumination

Au

Experiment 4

BFO
Au
BFO2

The side of the ilumination is relevant because the

photocurrent is assymetric (due to thermoelectricity,
probably)

Results
The current without light decreased to 0.1 pA
Same zero-bias photocurrent direction in both sides
Much more intense with high energy light

Photovoltaic effect has been demonstrated

Right-left asymmetry may result from a thermoelectric
power effect and/or uncontrolled asymmetries in the
configuration

Au

Experiment 5

BFO
Au
BFO2

The angle between the sample and Polarizer affects too

Blue Circles: Initial position
Green Circles: Initial position + polarizer rotation of 90

Results
The PV effect is maximum when the polarized-light
electric field is parallel to the in-plane component of
ferroelectric polarization (=90)
The PV effect is minimum when the polarized-light
electric field is perpendicular to the in-plane
component of ferroelectric polarization (=0)
After the rotation by 90, the change of photocurrent is
similar, except for a 90 phase

Conclusions
Diodelike behavior and Photovoltaic effect has been
shown

When a electical field larger than the coercitive field is

applied the diode polarization switches

The zero bias photocurrent density is side dependent

Constructive criticism
Are the samples truly monodomains?

Images could be better explained

Is the current density proportional to length?