Photovoltaic mechanisms in ferroelectric thin films with the effects of the electrodes

and interfaces
Meng Qin, Kui Yao, and Yung C. Liang

Citation: Applied Physics Letters 95, 022912 (2009); doi: 10.1063/1.3182824

View online: http://dx.doi.org/10.1063/1.3182824
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 APPLIED PHYSICS LETTERS 95, 022912 共2009兲

Photovoltaic mechanisms in ferroelectric thin films with the effects

of the electrodes and interfaces
Meng Qin,1,2 Kui Yao,1,a兲 and Yung C. Liang2
1
Institute of Materials Research and Engineering (IMRE), A*Star (Agency for Science,
Technology and Research), 3 Research Link, Singapore 117602, Singapore
2
Department of Electrical and Computer Engineering, National University of Singapore, Kent Ridge,
Singapore 119260, Singapore
共Received 21 May 2009; accepted 23 June 2009; published online 17 July 2009兲
It was discovered that the dielectric constant of the electrodes substantially determines the
photovoltaic output in 共Pb0.97La0.03兲共Zr0.52Ti0.48兲O3 ferroelectric thin films. With the screening
charges distributed extensively away from the electrode interfaces, the use of the electrodes with a
high dielectric constant gives rise to dramatically enhanced magnitude of photocurrent in
photovoltaic thin films, and extremely high photovoltaic efficiency is theoretically predicted to be
possible in ferroelectric ultrathin films or nanostructures. © 2009 American Institute of Physics.
关DOI: 10.1063/1.3182824兴

Ferroelectric materials, which exhibit strong bulk photo-
voltaic effect, have not been widely explored for photovol-
taic device applications, and even the mechanism of ferro-
electric photovoltaics has not been well understood. In the
early years, a few reports suggested that the photocurrent in
ferroelectrics arises from delocalized band-to-band optical
transition in polar crystals due to Frank–Condon relaxation
of the excited state.1,2 It was also reported that the appear-
ance of photocurrent in ferroelectrics is due to the asymmet-
ric momentum distribution of photoexcited carriers in non-
centrosymmetric crystals.3 Another point of view on the
nature of ferroelectric photovoltaics is the nonlinear property
of the dielectrics under UV radiation.4,5 Many investigators
believe that ferroelectric photovoltaic effect is induced by the
depolarization electric field which separates the photogener-
ated charge carriers.6–11 In all these previous theories, how-
ever, an important factor which determines the depolariza-
tion field—screening effect is neglected. The ferroelectric
polarization is not able to exist stably without charge screen-
ing, and the screening charge generally cancels the depolar-
ization field.12–16 Therefore, previous models involving the
depolarization field cannot well explain the photovoltaic be-
haviors in ferroelectric thin films. Here we establish a gen-
eral physical model taking into account the ferroelectric po-
larization, the screening effect, and the electrode interfacial
energy barriers as well, to elucidate the mechanism of pho-
tovoltaics in ferroelectric thin films.
The model is developed on the basis of charge distribu-
tion ␳共x兲 共C / cm3兲 in ferroelectric sandwiched between two
electrodes, including polarization charge, Schottky space
charge, and screening charge in the electrodes, as shown in
Fig. 1. In this case, the internal electric field in the ferroelec-
tric film E共x兲 can be determined by Poisson equation

冦 冧
qNeff1x/共␧0␧r兲 − P/共␧0␧r兲 + E共0兲 共0 ⬍ x ⬍ w1兲
E共x兲 = 冕 ␳共x兲
␧ 0␧ r
dx = qNeff1w1/共␧0␧r兲 − P/共␧0␧r兲 + E共0兲 共w1 ⬍ x ⬍ w2兲
qNeff2共x − w2兲/共␧0␧r兲 + qNeff1w1/共␧0␧r兲 − P/共␧0␧r兲 + E共0兲 共w2 ⬍ x ⬍ L兲,
共1兲

where ␧0 is the dielectric constant in vacuum, ␧r is the rela-
tive dielectric constant of the ferroelectric film, and E共0兲 is
the electric field at x = 0. In the electrodes, the electric field
Ee共x兲 and screening charge n共x兲 or p共x兲 obey the equations
below
Poisson equation:dEe共x兲/dx = − qn共x兲/共␧0␧e兲
= qp共x兲/共␧0␧e兲,
Ee共x兲 = − dVe共x兲/dx, 共4兲
where ␧e is the dielectric constant of the electrode, ni is the
equilibrium carrier density in the electrode, k is Boltzmann
constant, T is absolute temperature, and Ve共x兲 is the potential
distribution in the electrode. With boundary conditions 共dis-
placement continuity at interfaces, short circuit 0 potential
共2兲 across the film兲 and steady state current continuity equation

Boltzmann law: 再 n共x兲 = ni exp关qVe共x兲/共kT兲兴

p共x兲 = ni exp关− qVe共x兲/共kT兲兴,
冎 共3兲 dn共x兲/dt = 共1/q兲共dJn共x兲/dx兲 + G共x兲 − Rn共x兲 = 0, 共5兲

where G共x兲 and Rn共x兲 are the electron generation and recom-
a兲
Author to whom correspondence should be addressed. Electronic mail: bination rates under illumination, respectively, and Jn共x兲 is
k-yao@imre.a-star.edu.sg. the photocurrent in the ferroelectric film, the short circuit

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 022912-2 Qin, Yao, and Liang Appl. Phys. Lett. 95, 022912 共2009兲

FIG. 1. 共Color online兲 Schematic for the distribution of charge density ␳共x兲
in the electrode-ferroelectric-electrode sandwich structure. Space charges
qNeff1 and qNeff2 distribute uniformly in the Schottky space charge region
共SCR兲 0 ⬍ x ⬍ w1 and w2 ⬍ x ⬍ L. Polarization charges +P and −P distribute
at the interfaces x = L and x = 0, respectively. The surface screening charges
Q1 and Q2 共Coulomb兲 distribute in the top and bottom electrodes, L1 ⬍ x
⬍ 0 and L ⬍ x ⬍ L2, respectively.

photocurrent under UV illumination can be numerically cal-

culated accordingly.
The experimental data and simulation results of the
thickness-dependent short circuit photocurrent 共Jsc versus L兲
for the LSMO/PLZT/Nb:STO, Au/PLZT/Nb:STO, and Au/
PLZT/Pt thin films are shown in Fig. 2. The preparation de-
tails were presented in previous papers,17,18 and simulation
parameters are provided in Ref. 19. The simulation results
predict that there is an optimum thickness Lpeak at which the
maximum photocurrent occurs for the ferroelectric thin
films. The magnitude of photocurrent Jsc increases with the
decrease in film thickness above the thickness Lpeak, but
drops with the further decrease of thickness below Lpeak.
The epitaxial LSMO/PLZT/Nb:STO and Au/PLZT/
Nb:STO showed much larger photocurrent than that in poly-
crystalline Au/PLZT/Pt because the epitaxial crystalline
structure with minimized defects improved the lifetime of
the photoinduced charge carriers and the larger depolariza-
tion field due to the larger polarization could separate the FIG. 3. 共Color online兲 Simulation results of the effect of ␧e1 and ␧e2 on 共a兲
electron and holes more effectively to enhance the photovol- Jsc and 共b兲 Lpeak in PLZT thin films. The width of Schottky space charge is
taic output. wSCR = 5 nm in the simulation.
What is more interesting is that the experimental data
in Fig. 2 show that the LSMO/PLZT/Nb:STO exhibited sig- high-dielectric-constant electrode 关e.g., conductive oxides
nificantly larger photocurrent than Au/PLZT/Nb:STO, al- ␧LSMO ⬇ 800 共Ref. 22兲 and ␧Nb:STO ⬇ 1000 共Ref. 23兲兴 tends to
though the conductivity of Au 共4.52⫻ 105 S / cm兲 is much have the screening charges more extensively distributed
higher than that of LSMO 共1029.87 S/cm兲. Our theoretical away from the interface and consequently the polarization
analyses showed that the dielectric constant of the electrode screening effect is weakened. This should be the reason why
significantly influenced the screening charge distribution and the LSMO/PLZT/Nb:STO with perovskite LSMO top elec-
the photovoltaic output 共see Ref. 19兲. The low-dielectric- trode had much larger photocurrent than Au/PLZT/Nb:STO,
constant electrode 关e.g., metals ␧Au ⬇ 6 共Ref. 20兲 and ␧Pt as shown in Fig. 2.
⬇ 8 共Ref. 21兲兴 tends to have the screening charges more con- Photocurrent simulations were conducted for the ferro-
centrated near the ferroelectric-electrode interface and thus electric films with different combinations of the electrodes
polarization is screened more severely. On the contrary, the with different dielectric constants 共␧e1 and ␧e2兲. Based on the
simulation results, the relationship between dielectric con-
stant of electrodes 共␧e1 and ␧e2兲 and the magnitude of peak
Jsc are summarized in Fig. 3共a兲. At a fixed ␧e2, the magnitude

FIG. 2. Experimental and simulation results of the thickness-dependent

short circuit photocurrent Jsc in the LSMO/PLZT/Nb:STO, Au/PLZT/ FIG. 4. Simulation results for thickness-dependent short circuit photocurrent
Nb:STO, and Au/PLZT/Pt thin films. The incident UV wavelength and in- and photovoltaic efficiency in the extreme condition: ␧e1 → ⬁, ␧e2 → ⬁, and
2
tensity
This article is were 365 nm as
copyrighted andindicated
0.26 mW/ the, article.
incm respectively. wSCR
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 022912-3 Qin, Yao, and Liang
of peak Jsc increases with the increase of ␧e1. However, when
␧e1 is sufficiently large, the magnitude of peak Jsc saturates at
a constant level due to the space charge region 共SCR兲-limited
regime. In addition, the relationship between ␧e1, ␧e2 and
Lpeak is summarized in Fig. 3共b兲. At a fixed ␧e2, the Lpeak
decreases with the increase of ␧e1. However, when ␧e1 is
sufficiently large, Lpeak also stops to decrease at the thickness
of 2wSCR due to the SCR-limited regime. In a word, the
magnitude of peak Jsc increases while the Lpeak decreases
with larger dielectric constant of electrode 共␧e1 and/or ␧e2兲.
In our simulation, we noticed that all the Lpeak are either
larger than or equal to 2wSCR with different combination of
␧e1 and ␧e2. When Lpeak ⬎ 2wSCR 共␧e1 and/or ␧e2 is relatively
small兲, the drop of photocurrent with thickness reduction
共below the thickness Lpeak兲 is related to the screening effect
in the electrode, wherein both the peaks Jsc and Lpeak are
determined by ␧e1 and ␧e2. However, when ␧e1 and/or ␧e2
reach certain values, the maximum photocurrent invariably
occurs at the thickness of 2wSCR and that the peak Jsc satu-
rates according to our simulations, i.e., when wSCR = 5 nm,
the maximum Jsc occurs at Lpeak = 2wSCR = 10 nm in Fig.
3共b兲, and peak Jsc keeps constant at 3.44 ␮A / cm2 in Fig.
3共a兲. Even though the ␧e1 and/or ␧e2 continue to increase, the
Lpeak stops to decrease and keeps constant at the thickness of
2wSCR, as shown in Fig. 3共b兲. In this case, the top and bottom
SCRs occupy the whole film thickness without so-called
bulk ferroelectric film region. With the opposite direction of
the electric field at the top and bottom SCRs, their superpo-
sition results in a canceling-out effect and thus the photocur-
rent drops quickly when the film thickness is below 2wSCR.
In this case, the drop of photocurrent with thickness reduc-
tion 共below the thickness Lpeak兲 is due to the SCR effect
rather than the screening effect. Thus, for Jsc and Lpeak in Fig.
3, there are two different limitation regimes: screening-
limited regime when ␧e1 and/or ␧e2 are relatively small, and
as SCR-limited regime when ␧e1 and/or ␧e2 are relatively
large. In the screening-limited regime, screening effect is
more severe due to the small value of ␧e1 and/or ␧e2 共metal
electrode兲, and the magnitude of Jsc and Lpeak are determined
by the dielectric constant of electrodes 共screening effect兲.
When ␧e1 and/or ␧e2 become large 共conductive oxide elec-
trode兲 and the screening effect becomes weak enough, the
SCR-limited mechanism can take the dominant effect in de-
termining the magnitude of Jsc and Lpeak, leading to a satu-
rated magnitude for the peak Jsc and constant Lpeak 共Lpeak
= 2wSCR兲.
When it comes to the extremely ideal condition, the di-
electric constant of electrode is infinitely large 共␧e1 → ⬁ and
␧e2 → ⬁, no screening effect兲 and SCR width goes to 0
共wSCR = 0, Ohmic contact at interfaces兲, our simulation result
in Fig. 4. shows that the photocurrent continuously increases
with the reduction of film thickness without a peak-
photocurrent and that light-to-electricity photovoltaic effi-
ciency also increases with the reduction in the film thickness.
It has been reported that ferroelectricity possibly persists
down to the thickness of 3 unit cells 共1.2 nm of PLZT兲.24,25
According to Fig. 4, the theoretically predicted photocurrent
is 288.52 ␮A / cm2, and the corresponding photovoltaic effi-
ciency can be as high as 19.5% at the thickness of ⬃1.2 nm.
Recently, a photovoltaic efficiency in the order of ⬃0.1%,
which was about two orders of magnitude higher than the
bulk ferroelectrics, was experimentally demonstrated in a
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Appl. Phys. Lett. 95, 022912 共2009兲
ferroelectric PLZT thin film of 68 nm in thickness.18 The
theoretical analyses here indicate the great room to further
improve the photocurrent and photovoltaic efficiency in
ferroelectric ultrathin films or nanostructures when the
screening effect could be minimized and the interfacial
Schottky barrier could be eliminated.
In summary, it was discovered through both the theoret-
ical and experimental approaches that the dielectric constant
of the electrodes substantially determines the photovoltaic
output of ferroelectric thin films. With the screening charges
distributed extensively away from the interface between the
ferroelectric and electrodes, the use of the electrodes with a
high dielectric constant gives rise to dramatically enhanced
magnitude of photocurrent. Extremely high photovoltaic ef-
ficiency up to 19.5% is theoretically predicted as possible in
ferroelectric ultrathin films or nanostructures when the
screening effect could be minimized and the interfacial
Schottky barrier could be eliminated. It should be noted that
intriguing photovoltaic output has also just been reported in
ferroelectric BiFeO3 bulk single crystal under visible light
although the currently obtained photovoltaic response is very
low.26 The insight gained here provides a general strategy to
further improve the efficiency of various photovoltaic de-
vices by implementing nanostructures and taking into ac-
count both the photovoltaic materials and their electrodes as
a whole.
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