Review
Hall of Fame Article
Barium Titanate Nanostructures and Thin Films
for Photonics
Artemios Karvounis,* Flavia Timpu, Viola V. Vogler-Neuling, Romolo Savo,
and Rachel Grange*
Barium titanate (BaTiO3) is a synthetic crystal used in electromechanical
transducers and multilayer ceramic capacitors. Since it is not available in
nature, a variety of growth methods has been employed to produce in large
scale, with high quality and low-cost. BaTiO3, as a metal oxide meets practical
requirements such as physical hardness, stability and tunable optoelectronic
properties. The plethora of characteristics renders it functional in diverse
fields of applications from energy harvesting to biophotonics. Related to
optical properties, it is a dielectric material from the near ultraviolet to the
near-infrared part of the spectrum with low optical losses and relatively high
refractive index. The strong second-order nonlinear response has resulted in
several breakthroughs in bioimaging, while its intrinsic electrooptic response
is among the highest within the existing materials. The properties of the
BaTiO3 may also be modified by doping or hybridization with other materials.
This review presents the basic optoelectronic properties of BaTiO3, reports
on the recent advances in BaTiO3 nanostructures and thin films related to
photonic applications, and oversees photonic technologies that may benefit
from this material platform in the near future.
1. Introduction
The fast evolution of information technology requires mate-
rials and architectures that can handle and retrieve data at short
time scales and with the minimum power consumption. As the
complexity and amount of data across the network increase rap-
idly, more reliable devices with small physical and energy foot-
prints are needed. Photonic nanostructures and thin films are
Dr. A. Karvounis, Dr. F. Timpu, V. V. Vogler-Neuling,
Dr. R. Savo, Prof. R. Grange
Optical Nanomaterial Group
Institute for Quantum Electronics
Department of Physics
ETH Zurich
Zurich 8093, Switzerland
E-mail: karvounis@phys.ethz.ch; grange@phys.ethz.ch
The ORCID identification number(s) for the author(s) of this article
can be found under https://doi.org/10.1002/adom.202001249.
© 2020 The Authors. Published by Wiley-VCH GmbH. This is an open
access article under the terms of the C
­ reative Commons Attribution-
NonCommercial License, which permits use, distribution and reproduc-
tion in any medium, provided the original work is properly cited and is
not used for commercial purposes.
DOI: 10.1002/adom.202001249
Adv. Optical Mater. 2020, 8, 2001249 2001249  (1 of 23)
www.advopticalmat.de
expected to fulfil those demands. Upon
squeezing of light in volumes comparable
or even smaller than its wavelength, light
can experience interactions stronger or
even different than propagating in bulk
materials.[1] In this context, functional
optical materials that have minimum
optical losses, large optical nonlineari-
ties and fast response time to external
stimulus have been the epicenter of a
continuous research over the past years.
First, plasmonic metals have appeared
as a promising platform to focus light
in deeply subwavelength spots and have
offered several breakthroughs.[2–7] Despite,
the extreme control of light by plasmonic
resonators, the accompanied losses asso-
ciated with radiative and nonradiative
dissipation have placed a barrier on their
evolution into commercial products. In
contrast, optically dielectric materials
like silicon, a CMOS compatible material
served as an enabling platform toward the
same goal.[8–11] Despite silicon’s high refractive index and low
loss in the near-infrared, optical properties are mostly fixed with
limited nonlinear and electrooptic responses, related to thermo-
optic and doping effects. Thereby, it has been a continuous
effort to explore materials with active properties.[12–16] Among
others, barium titanate (BaTiO3) with intrinsic optical ultrafast
nonlinearities, electrooptic response and physical endurance
can be a platform to realize intelligent computing architectures
that reconfigure light at short time scales.
Over the last 30 years, both top-down and bottom-up fabri-
cation methods are employed to produce BaTiO3 in the form
of thin films or nanostructures, respectively. Both fabrication
types are compatible with the efficient doping of BaTiO3 to
improve its functionalities. This exceptional material platform
sets the framework for numerous breakthroughs in a diver-
gent range of photonic applications. In this review, we will go
through the physical properties of BaTiO3 up to the latest opto-
electronic research based on this material platform. The future
prospects are mentioned in the last part of this review. Part 2 is
an overview of the physical properties of BaTiO3. In Sections 2.1
and 2.2 the impact of crystal’s symmetry on the optoelectronic
behavior, as well as the basic fabrication methods of BaTiO3
are presented, respectively. The linear optical (Section  2.3),
the electrooptic (Section  2.4) and nonlinear optical properties
(Section 2.5) of BaTiO3 are also reviewed. Furthermore, the doping
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Figure 1.  BaTiO3 films and resonant nanostructures for photonics. Doped films for light generation and nonlinear modification of BaTiO3 optical
properties (Section 2.6). Thin films of BaTiO3 grown by top-down methods for integrated electrooptic modulators (Section 3). BaTiO3 nanoparticles
and nanowires are utilized for nonlinear optics and biophotonics; hybrid BaTiO3/plasmonic nanoparticles employed for enhanced optical nonlinearities
(Section 4.1). Photonic metamaterials made from: BaTiO3 arrays of nanodisks, BaTiO3 nanoparticle films and metallic gratings or nanoparticles and
nanowires embedded in BaTiO3 matrix (Section 4.2). Photonic crystals such as woodpile 3D structures are used for nonlinear optics (Section 4.3). The
interaction length L is presented for every type of structure.

of BaTiO3 with different types of dopants and the THz response
is presented in Sections 2.6 and 2.7, respectively. In part 3, inte-
grated electrooptic modulators of BaTiO3 thin films are pre-
sented. Special emphasis is given in the performance of the
devices and the intricacies related to the film growth of BaTiO3
via top-down methods. In part 4, the photonic applications
related with nanostructured BaTiO3 in the form of nanoparti-
cles (Section 4.1) and in the form of nanostructured thin films
such as metasurfaces (Section 4.2) and photonic crystals (PhCs)
(Section  4.3) are presented. Several fields of research employ
BaTiO3 nanostructures such as biophotonics or nonlinear
optics and electrooptics. Figure  1 captures the main schemes
where BaTiO3 nanostructures and films are utilized up with the
corresponding interaction length, L. Last, an overview of var-
ious applications that may benefit from this enabling material
platform is presented.
2. Physical Properties of BaTiO3
2.1. Structural Properties of BaTiO3
Since the theoretical prediction of BaTiO3 in 1926, by Gold-
schmidt,[17] 15 years had to pass for the production of this
crystal. It was 1941, when an American company filed the first
patent of synthesizing BaTiO3 to protect the breakthrough
of this high permittivity ceramic.[18] They produced the syn-
thetic crystal after doping TiO2 with BaO, which improved
the permittivity of TiO2 (εr  ≈ 80) by more than ten times by
(εr  > 1000).  BaTiO3 has a ferroelectric state at room tempera-
ture, which exist up to the Curie temperature (TC). Until the
mid-40s, ferroelectricity was considered to be a property associ-
ated with hydrogen bonded media. The study of ferroelectricity
by Von Hippel (USA) also included ceramics such as BaTiO3
in the class of materials with ferroelectric properties.[19] The
spontaneous polarization in ferroelectric materials results to a
noncentrosymmetric (acentric) unit cell. For temperature below
the Curie point, namely below TC  = 120  °C for bulk BaTiO3
crystal, the unit cell possesses a tetragonal (P4mm) symmetry
and thereby is noncentrosymmetric.[20]
BaTiO3 belongs to the class of perovskites, similar to the
mineral CaTiO3, with the general formula of ABX3. Sites A and
B are filled by metals, while the X site is occupied by a nonme-
tallic element such as oxygen, forming the ABO3 structure. For
BaTiO3, the Ba+2 cations are located on the A-sites and Ti+4 on
the B-sites. The relative position of each ion within a single
unit cell is schematically presented in Figure 2, with eight Ba+2
being on the corners at (0 0 0); (0 0 1); (0 1 0); (1 0 0); (1 0 1);
(1 1 0); (0 1 1); (1 1 1). In cubic symmetry, the Ti+4 cations are
positioned in the center at (½, ½, ½), while six O− anions are
at the center of the four faces at (0, ½, ½); (½, 0,½); (½, ½, 0).
Between Ba+2 and TiO3 group are formed ionic bonds, while

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Figure 2.  Crystal structure symmetry and temperature-phase diagram of
BaTiO3. a) Noncentrosymmetric unit cell structure of BaTiO3 for tetrag-
onal phase (below Curie temperature); centrosymmetric unit cell structure
of BaTiO3 for cubic phase (above Curie temperature), b) variation of the
cube root of the volume of the cell with temperature for various phases of
BaTiO3. (b) Adapted under the terms of a Creative Commons Attribution
CC-BY license.[23] Copyright 2010, The Authors, published by MDPI.
covalent bonds are formed between Ti and O atoms. Since ionic
bonds are stronger than covalent bonds, the role of Ba cannot
be used to tune the macroscopic optoelectronic properties of
the crystal.[21] In contrast, the covalent bonding between the
titanium and oxygen can go through several types of control
and defines several properties such as the energy bandgap, the
refractive index and the polarization strength of BaTiO3.
BaTiO3 at room temperature has tetragonal symmetry, where
titanium and oxygen are displaced along the elongated axis (c-axis)
in opposite directions. However, when temperature is above the
TC the unit cell turns to cubic symmetry (Pm3m), where ions
take symmetric positions. This transition is first order, there-
fore several properties such as the electric permittivity, the lattice
constant and the polarizability manifest a discontinuity upon
crossing the Curie temperature. The tetra­gonal symmetry (a cube
that has been elongated in one direction) stems from the displace-
ment of the titanium ions from the center of the unit cell, thus

giving a net dipole moment (P ), see Figure 2b. The elongated axis
is called c-axis, while the other two axis (a and b) are annotated as
a-axis, due to the equal length they have, in the tetragonal phase.
BaTiO3 has a series of ferroelectric to ferroelectric transitions
from (P4mm) tetragonal → (Bmm2) orthorhombic, which takes
place at 5 °C and a transition from orthorhombic to (R3m) rhom-
bohedral
 at −90 °C.[22,23] In these phases, an intrinsic polarization
P appears, with an orientation that changes at the transitions. For
the tetragonal phase, P is parallel to the edge of the crystal unit
cell, while for the orthorhombic (a  = c  < b) and rhombohedral
(a = b = c) phases it becomes parallel to the face diagonal and the
body diagonal, respectively.)
Every linear and nonlinear process taking place on BaTiO3 is
related to the microscopic properties of the crystal. As a result,
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even sub-nm displacement of the relative position of ions result
to macroscopically observed optoelectronic changes, thereby
offers a scheme for passive and active tuning of material
properties in a range of nanophotonic applications from light
generation up to electrooptic modulation. Similar responses (of
different strength) apply to crystals with the perovskite struc-
ture ABO3 like SrTiO3 or KNbO3 which belong in the same
family of oxygen octahedral ferroelectric structures.
2.2. Fabrication Methods of Films and Nanostructured BaTiO3
2.2.1. Thin Film Fabrication of BaTiO3
Several deposition techniques of epitaxial films have been
developed so far. The growth methods of thin films adequate
for optoelectronic applications, are based on high fidelity tech-
niques such as: molecular beam epitaxy (MBE)[24,25] and atomic
layer deposition (ALD),[26] or other types of deposition such
as: chemical vapor deposition (CVD),[27,28] pulsed laser deposi-
tion (PLD),[29–31] radio-frequency (RF) sputtering[32] or sol–gel
methods.[33] The BaTiO3 crystal quality depends strongly on the
substrate onto which the layer is grown as well as the deposition
technique. A critical parameter for obtaining monocrystalline
layers is the lattice match between the substrate and the BaTiO3
layer. Parameters like defects, strain, grain size, etc. affect
directly the linear and nonlinear optical properties of BaTiO3.
The closer these values are to the bulk values, the higher the
film quality is. Based on these criteria, the highest quality
BaTiO3 thin layers are produced by MBE growth, where a lat-
tice matched buffer layer is used.[34] Even in these conditions,
grains in the layer have lateral sizes of 20 to 30 nm. Then, ALD,
PLD, and MOCVD can produce films with properties quite
close to the bulk. In the absence of the buffer layer, BaTiO3 thin
layers are generally polycrystalline or amorphous.[31]
Apart from the choice of material substrate, parameters like
oxygen pressure or substrate temperature have large impact
over the conductivity or the c-axis orientation, respectively.[35,36]
Samples that deviate from stoichiometric composition are not
anymore perfect dielectrics, while the deposition temperature
may produce films with large stress and ferroelectric polarization.
Despite their excellent optical properties, metal oxides such
as BaTiO3 are not usually considered for top-down fabrica-
tion because of difficulties in the etching process. Ferroelec-
tric metal oxides are inert to most chemicals, which strongly
limits the usage of wet chemistry methods for efficient etching
(etch rates below 1 nm min−1) compared to CMOS processes.[37]
Thereby hybridizing films of BaTiO3 with other CMOS compat-
ible materials such as silicon or silicon nitride is more common
to produce integrated electrooptic modulators.[38,39]
Vacuum-based deposition techniques suffer from high costs
and produce films with sub-micrometer thickness. Wet chem-
istry-based bottom-up approaches are superior in terms of cost,
surface areas, and thicknesses of the films.[40] In general, there
are two main approaches with bottom-up fabrication of BaTiO3
thin films, either diverse sol–gel techniques or BaTiO3 nanopar-
ticle solutions.
Sol–gel processed barium titanate thin films often start from
the precursors barium acetate and titanium(IV) isopropoxied,
which changes phase from amorphous to crystalline at
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700  °C.[41] As conventional integrated semiconductor circuits
do not stand such high temperatures, sol–gel techniques with
lower processing temperatures down to room temperatures are
of high interest.[42]
Sol–gel techniques are also limited to film thicknesses
of a few microns due to solvent evaporation and suffer from
biphasic amorphous crystalline structures as well as from an
unstable phase. To achieve thicker structures films of BaTiO3
are fabricated from solutions of nanoparticles. Either doctor
blading or spin-coating of nanoparticles with intermediate
drying have been utilized to develop ceramic capacitors with
high dielectric constants.[43] Moreover, nanoparticles combined
with polymers improve the dielectric properties of the nano-
composite polymer.[44,45]
2.2.2. BaTiO3 Nanoparticle Fabrication
BaTiO3 can also be produced in a nanostructured form, uti-
lised in a variety of applications. BaTiO3 nanoparticles have
been successfully synthesized by bottom-up wet chemistry
techniques that result in powders of nanoparticles. These
powders of BaTiO3 are used in electronic devices such as
multilayer ceramics with high crystallinity, purity and no
agglomerations. Initially, BaTiO3 powders were fabricated
using solid-state methods, which involve the slow reaction
of barium carbonate (BaCO3) and titanium oxide (TiO2) at
high temperatures of 1200  °C.[46] The powders produced by
this method contain large particles with a wide size distri-
bution and many agglomerations. Salt-assisted spray pyrol-
ysis (SASP) is another method for powder synthesis, which
requires fewer steps than the solid-state method and results
in nanoparticles with better homogeneity. The main step of
SASP is the use of an ultrasonic aerosol atomizer to spray a
precursor in a ceramic heated tube at 600–1000  °C. BaTiO3
nanoparticles with sizes from 30 to 360  nm can be fabri-
cated by SASP.[47] Wet chemistry methods make it possible to
synthesize particles at low temperatures, while allowing for a
better control of the molecular precursors. The obtained pow-
ders are fine, with nanoparticles smaller than 50  nm, pure,
homogenous, and of good crystalline quality. Several methods
have been developed specifically for BaTiO3 nanoparticles syn-
thesis: hydrothermal synthesis,[48] soft-chemistry with alkali or
alkaline earth metal,[49] molten-salt synthesis methods,[50] or
high energy ball milling.[46]
2.3. Linear Optical Properties of BaTiO3
BaTiO3 has a bandgap energy of ≈3.2  eV and does not sup-
port low-energy excitons, thereby it is an optical dielectric
with a weakly dispersive, moderate refractive index ≈2.5 and
negligible optical losses at visible and near-infrared wave-
lengths.[21] It is an adequate material platform to be utilized
both in photonic waveguides due to small optical losses, as
well as for resonant nanostructures such as photonic metas-
urfaces, photonic crystals, and other nanostructures, owing
to the large refractive index contrast in comparison to avail-
able substrates like quartz. In the single crystal form, the
tetragonal phase results in birefringent optical properties.
The difference between the ordinary (no) and the extraor-
dinary (ne) refractive index stems from the different length
of the c- and a-axis, where the a-axis has a lattice con-
stant a  = b  = 3.991 Å and c-axis has a constant of 4.035 Å.[20]
For light polarized along the a- or b- axis no is 2.40, while for
light polarized along the c-axis, ne  = 2.34 at 660 nm.  The dif-
ference between no and ne tends to zero as the temperature of
the crystal approaches the Curie temperature, TC. Buse et al.[51]
have shown that there is a small influence on no upon heating
toward TC, starting from room temperature. In contrast, the ne
becomes larger and approaches no for increasing temperatures.
The birefringence (ne – no) for different light wavelengths λ
and temperatures T is shown in Figure  3. The line fit of the
refractive index is described by the Sellmeier Equation[52]

Figure 3.  Optical refractive index of BaTiO3. a) Birefringent optical response of BaTiO3 bulk crystal; refractive index measured across the visible
spectrum, for light polarized along (no) and perpendicular (ne) to the a-axis. b) Refractive index deviation (ne − no) between opposite polarizations
over temperature. (a,b) Adapted with permission.[51] Copyright 1993, Wiley-VCH. c) Refractive index of BaTiO3 thin films (sub-micrometer thickness)
produced by different fabrication methods. The refractive indices data are obtained from the references as indicated: molecular beam epitaxy (MBE),[53]
pulsed laser deposited (PLD),[54] amorphous barium titanate fabricated by a sol–gel technique,[56] polycrystalline (poly-C) and amorphous sputtered
thin films of 1–5 µm thickness,[59] nanoparticle films deposited by spin-coating of solvothermal synthesized particles of a diameter of 5 nm (circles)[57]
and hydrothermally grown (triangular) of a diameter of 50 nm.[58]

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Figure 4.  Tunable optoelectronic properties of BaTiO3. a) Energy bandgap diagram of bulk BaTiO3. The p-orbitals of oxygen electrons form the valance
band (VB) of the crystal. Empty electron sites from titanium d-orbitals form the lowest energy of the conduction band. Oxygen vacancies contract the
bandgap energy, in contrast thinner films expand the bandgap energy. b) Absorption coefficient α spectra are modified as the crystal thickness; bulk
(green), 20 (blue), 11 (purple), and 8 nm (magenta) film, data obtained from ref. [61]. c) Electric resistivity over temperature of reduced BaTiO3−x with
different carrier concentration; more than ten orders of magnitude resistivity change is induced by the oxygen reduction from stoichiometric BaTiO3
to BaTiO3−x. Annotated is the carrier density of heavily reduced films. Data collected from ref. [67].

Bλ 2 on the bandgap energies. This is also explained by the closeness

n 2 (λ ) − 1 = A + (1)
λ2 − C
where A, B, and C are coefficients used as fitting para­­
meters. From these measurements, the thermo-optic coefficient
∂ne/∂T  = 1.8–5.6 × 10−4 K−1 is also deduced across the visible
wavelength range.
The plethora of methods used to grow BaTiO3 films may
induce modification on the refractive index. This variation is
related to parameters like extrinsic defects, grain size, porosity,
and deviation from stoichiometric BaTiO3. The refractive index
for different deposition methods is illustrated in Figure 3c. The
highest refractive index is achieved via molecular beam epi-
taxial growth.[53] Then, methods associated with the use of PLD
systems[54] or metal organic chemical vapor deposition[55] show
reduced refractive indexes, whereas sol–gel[56] and nanopar-
ticle-films[57,58] have the smallest value of the refractive index.
The decreased refractive index comes from the deviation of a
pure monocrystalline film. As a result, for samples produced
by sputtering or sol–gel, a post-annealing treatment is required
to improve the film crystallinity.[59] As shown in Figure 3c, the
nanoparticle films have the smallest refractive index. Generally,
films with smaller nanoparticle size are more closely packed, as
smaller gaps between the nanoparticles lead to higher refractive
indices.
The photo-excited electrons in semiconductors may form
either bound electron–hole pairs, called excitons or create free
carriers. Thereby, macroscopic properties such as the optical
dielectric response are directly related with the optical bandgap
and other low energy band-edge states of the crystal. The refrac-
tive index of BaTiO3 below the bandgap energies relies on
the strong transition from the 2p orbitals of oxygen and the 3s
orbitals of titanium atoms (4.4  eV) at the X point of Brillouin
zone.[21] Theoretical and experimental studies show that the
energy of the valence band (VB) is filled primarily from oxygen
2p atomic orbital, while the conduction band (CB) is derived from
the titanium 3d orbitals.[21,60] Barium atoms have less impact
of the absorption edge of BaTiO3 with SrTiO3 and TiO2, where the
absorption edge due to transitions between states has little admix-
ture of Sr or Ba wave functions. Various parameters like internal
stress or defects can tune the bandgap diagram of the crystal.
A schematic of the BaTiO3 bandgap diagram is shown in
Figure 4a. Defects associated with oxygen vacancies reduce the
bandgap energy of the crystal. At the same time, the bandgap
opens toward higher energies as the thickness of the crystal is
reduced. Chernova et al.[61] studied the effect of thickness/strain
on the optical absorption of epitaxially grown BaTiO3 and com-
pare the absorption spectra with bulk, 20, 11, and 8  nm thin
films. Every sample has absorption resonances around 8.5 and
5  eV, similar to previous reports.[21,52] These absorption corre-
sponds to two groups of electronic transitions from the VB to
the CB. The d band usually comprises a low and high energy
subband dε and dγ, respectively. The transition from the (VB)
to the dε and dγ are responsible for the peaks at 8.5 and at 5 eV,
respectively. The higher energy resonance remains similar for
every sample; therefore it is independent to the film thickness,
as it is presented in Figure  4b. In contrast, the spectral posi-
tion and the magnitude of the lower-energy peak in the films
develop with reducing the film thickness and/or increasing
strain. An additional remark is that the absorption edge blue-
shifts in the films in comparison to the crystal. Theoretical cal-
culations,[62] predict that the d conduction band levels are raised
to higher energies by the displacement of the titanium cations
toward the oxygen anion, whereas these conclusions are con-
firmed by first-principles analyses.[63,64] As a result, authors con-
cluded that the modification of the optical absorption is related
to the anisotropic lattice strain and proposed that the induced
strain of the films is responsible for the observed behavior.
Another parameter that affects the absorption of BaTiO3 is
the oxygen vacancies of the material. In contrast to previous
method, the oxygen reduction of stoichiometric BaTiO3 to
BaTiO3−x offers a platform to reduce the bandgap of the crystal.
More specifically, Zhao et  al.[65] explored the impact of oxygen

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pressure during deposition of BaTiO3 on the electrical and of the EO effect in BaTiO3 and define the constants and para­
optical properties of BaTiO3 thin films grown by laser mole­ meters, which will be useful to compare the performance of the
cular-beam epitaxy. It was shown that the electrical conductivity EO devices presented in Section 3.
of the BaTiO3−x is improved upon reducing the oxygen pressure When an external electric field E is applied on as single
during deposition, where a metallic response was observed. The crystal, the index ellipsoid (ηij(0) +  Δηij)xixj  = 1 is deformed
electrical resistivity measured for the oxygen deficient BaTiO2.52 into:
thin films was found to be three orders of magnitude larger
than most common metals and the lowest resistivity value 1 1 2 1  1   2 1 1 2
among literature for BaTiO3, namely 6.0  × 10−5  Ω cm at room  2 + ∆ 2  x +  2 + ∆ 2  y  2 + ∆ 2  z
 nx  
n 1  ny  
n 2   nz  n 3 
temperature. At the same time, the carrier density reached
1 1 1
values of 2  × 1022 cm−3 an order of magnitude lower than + 2∆  2  yz + 2∆  2  xz + 2∆  2  xy = 1
 n 4  n 5  n 6
metals. In addition, for every oxygen deficient BaTiO3−x film
was measured an optical absorption resonance. The absorption
spectral position blue shifts, while the linewidth becomes wider (2)
 r11 r23 r13 
with decreasing oxygen pressure.  
 r21 r22 r23   Ex 
Kolodiazhnyi used another approach to create oxygen vacan-
1 3
r31 r32 r33  E 
cies.[66] He used undoped BaTiO3 single bulk crystals, which where ∆  2  = ∑rij E k = 
 n i j =1  r41 r42 r43   y 
were reduced in temperatures higher than 900 °C in hydrogen    Ez 
r51 r52 r53
or nitrogen rich conditions. Such conditions improved the  
 r61 r62 r63 
carrier concentration to levels higher than 1018 cm−3. Fol-
lowing this process, the insulator–metal transition was found
at a critical electron concentration of nc  ≈ 1.6  × 1020 cm−3. In Here rij is the linear EO coefficient and r is the EO tensor.
a work followed 2 years later by Kolodiazhnyi et  al.[67] they Provided the crystal symmetry, several elements of the EO
tried to answer the question if metallic BaTiO3−x could retain tensor may have the same or opposite values, or even be zero.
ferroelectricity by identifying a series of low symmetry phase Specifically for BaTiO3 due to symmetry of the crystal we have
transitions in metallic BaTiO3−x that may support ferroelectric
phase. Since the hybridization between the titanium 3d states  0 0 r13 
and the oxygen 2p states is essential for ferroelectricity,[68] they  
 0 0 r23 
detect discontinuities in electrical resistivity over temperature 0 0 r33
rBaTiO3 =  (3)
and claim an indirect evidence of the low-symmetry crystallo-  0 r42 0 
graphic phase transitions in BaTiO3−x. In Figure 4c is presented  r51 0 0 
the temperature dependence of BaTiO3−x resistivity, for various  
 0 0 0 
electron concentration n. At the same time, Hwang et  al.[35]
explored the oxygen vacancy role on the optical properties over The crystallographic point group P4mm of BaTiO3 can
mid-IR light. They observed that the structural phase transi- explain the zero elements, while it is also r13 = r23 and r42 = r51.
tions had a direct impact on the infrared response. Metallic The Pockels tensor components[69] are given in Table 1.
ground state was confirmed by the Drude-type low-frequency In Table  1, are presented the EO tensor components of
optical reflectance, while the mid-infrared absorption band of BaTiO3 for clamped and unclamped crystals. The mechanical
BaTiO3−x appears and grows with an increase in the oxygen constraints on the crystal affect greatly the EO response. If
vacancy concentration. BaTiO3 is unclamped, an electric field will induce a deforma-
tion by the converse piezoelectric effect. In turn, a modification
of the refractive index is caused due to the photoelastic effect.
2.4. Electrooptic Effect in BaTiO3 As a result, the electrooptic effect measured for unstrained
crystals is called the primary effect, while the response due to
The strong electrooptic response of BaTiO3 makes it a prom- piezoelectricity and photoelasticity is then named the secondary
ising material platform for EO applications. Bulk BaTiO3 has effect.[70] The observed effect in a free crystal is the sum of the
the largest Pockels coefficient reported up to date, which is primary and secondary effects. Thereby, the EO effect can be
measured to be r42 = 1300 pm V−1 in the unclamped (zero-stress described through the following equation
case) and r42  = 730 pm V−1 in the clamped case, see Table  1.
In this part, we review the essential effects associated with the 1
∆  2  = rijkTE k + quadratic terms = rijks + ( pijlm dlmk )E k + ··· (4)
origin of this strong response, identify the microscopic origin  n i

Table 1.  BaTiO3 electrooptic tensor coefficients. where T and s indicate constant stress and strain, while p and
d are the photoelastic and piezoelectric tensors, respectively.[71]
EO coefficient Unclamped [pm V−1] Clamped [pm V−1] In Equation (4) rijkT and rijks are the free (unclamped) and clamped
r13 = r23 10.2 ± 0.6 8 ± 2 EO coefficients, respectively, while the product pijlmdlmk is the
r33 105 ± 10 40.6 ± 2.5
contribution to the electrooptic effect from the photoelastic
effect. Even though in several reports an effective coefficient
r42 = r51 1300 ± 100 730 ± 100
is used to describe the phenomenon, the separate coefficients

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provide an overview of the effects taking place in parallel. Esti- Table 2.  Optoelectronic characteristics of ABO3-type crystals. Refrac-
mations based on several physical effects suggest a weak reduc- tive index (at 633  nm); electrooptic coefficient rij (clamped case, i.e.,
constant strain); Curie transition temperature TC; dielectric constant εr
tion of the EO response in the infrared wavelength region and (orthogonal to polarization direction) for bulk ferroelectric oxides. The
different electrooptic response for clamped and unclamped values are measured at room temperature.
crystals.[69,72] For the clamped case (constant strain), the elec-
trooptic effect is two times smaller in comparison to the Material Refractive index r [pm V−1] TC [°C] εr Reference
unclamped case (constant stress), where photoelastic contribu-
LiNbO3 2.29 r33 = 31.8 1195 84 [73,74]
tions add to the generalized electrooptic effect, while the elastic
deformations are induced by the piezo-electric effect, which dis- BaTiO3 2.37 r42 = 730 120 4500 [69,74]

sipates at higher frequencies. LiTaO3 2.23 r33 = 31 610 51 [73,75]

Upon separation of the purely electronic contribution rijke PbTaO3 2.67 r33 = 5.9 490 115 [76,77]
from the clamped electrooptic coefficient becomes KNBO3 2.23 r33 = 64 435 160 [74]
BiFeO3 3 r33 = 12 1100 30–50 [78,79]
rijkT = rijke + rijko + rijka (5)

where rijko and rijka are associated to the optic and acoustic lattice
vibrations. The contributions are frequency dependent. For
more information on the EO effect, see Günter[71] from where
we adapted the annotations. The electronic contribution to the
electrooptic coefficient rijke can be determined from the nonlinear
optical susceptibilities dkji obtained, e.g., by second-harmonic
generation (SHG) experiments by using the following equation
4 trosymmetric crystals, with the perovskite structure ABO3.
rijke = dkji (6)
ni2 n 2j
where ni2 and n 2j , and rijke are the refractive indices and elec-
trooptic coefficients for the fundamental frequency. More
details on the physics of second-harmonic generation will
follow in the next Section.
From the index ellipsoid, an effective coefficient sufficient
can be derived to describe the linear electrooptic effect, such as
1 than thin films, which have process-dependent properties due
∆n (E ) = − reff n 3E (7)
2 to deviation in stoichiometry, the presence of defects, rough-
For traveling-wave EO phase modulators, the half-wave
voltage Vπ defines, for a specific geometry, the voltage needed
to induce a π phase shift for the transverse configuration
λd
Vπ = (8)
Lrn 3
Chen et  al.[82] suggested a model for predicting the clamped
EO coefficients of the crystals based on the relative displace-
ments of the central metal ion (B) to oxygen in the BO6 oxygen
octahedron. The aforementioned displacements modify the
wave functions of the electrons in the crystal through electron–
phonon coupling, which then induces a change of the refractive
index. The electrooptic effect of BaTiO3 is the highest recorded
in bulk materials, as presented in Table 2 over several noncen-
From Table 2 we can conclude that the optical refractive index
is not associated with the strength of the EO effect. Neither the
transition Curie temperature can be an index of the strength of
the EO effect. In contrast, the large dielectric constant is asso-
ciated with the strength of the EO effect, for an ABO3 type of
crystal. The larger the polarizability of the crystal, the longer
the displacement of B site, as a result there is space for larger
motion and thereby stronger modification of the refractive index.
Normally, bulk crystals have stronger electrooptic response
ness, grain boundaries, strain gradients, and domain struc-
tures. Thereby, it is clear that for reliable EO devices, we have to
understand how the processing methods affect the performance
of each material system. In part 3, the efforts and studies to
produce integrated EO devices out of nanofilms with EO coef-
ficient comparable to bulk crystals will be reviewed.

Here, λ is the wavelength, d is the electrodes distance, L
is the total interaction length, r is the EO coefficient, and n is
the refractive index. From Equation 8 it stems that low-voltage
modulators may have either large EO coefficient or long inter-
action lengths.
After presenting the mathematical formalism and the phys-
ical origin of the EO processes, we overview the advances of the
field over the last years. The first theoretical studies on the elec-
trooptic response crystals of perovskite structure were based
on phenomenological and semiempirical methods. Kurtz and
Robinson[80] used an anharmonic oscillator model, while Levine
employed a bond charge model.[81] Furthermore, Wemple and
DiDomenico Jr.[52,73] had managed to calculate the EO response
through the changes in the bandgap induced by the lattice
polarization and identified the origin of this response due to
the distortion of the BO6 oxygen octahedra. Similar to that,
2.5. Nonlinear Response from BaTiO3
2.5.1. Second-Harmonic Generation
Harmonic generation is a nonlinear optical process that
appears when the material is exposed to an external field with
a strength comparable to or higher than the atomic electric
e
field E atom = , where e is the charge of an electron and
4πε 0 a0
ao is the Bohr radius of a hydrogen atom.[83] Thus, the bound
electrons in the material have an anharmonic response and the
atomic dipole moments emit higher frequency secondary radia-
tion. This response can be modeled by introducing a nonlinear
polarization in the Maxwell equation, which contains additional
nonlinear terms and can be expressed as a series driving elec-
tric field powers (Equation (9))[83]

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addition to the full permutation symmetry, the Kleinman’s sym-

metry also applies. Second, the crystal symmetry of the material
leads to the cancelation of χ(2) components. Thereby, in the case
of tetragonal BaTiO3 at room temperature, the χ(2) susceptibility
reduced to a 6 × 3 matrix d, named reduced tensor, which has
three independent components (Equation (11))[86]

 0 0 0 0 d15 0 
d =  0 0 0 d15 0 0
 (11)

 d31 d31 d33 0 0 0 

and Equation  10 becomes P(2) = 2ε0dE2, where

Figure 5.  Nonlinear interaction between light and matter: Schematic
representation of quantum mechanical principle for a) second-harmonic
generation (SHG) and b) two photon excited fluorescence. For both inter-
actions, two photons with identical wavelengths (red) are involved. For
SHG, the two photons are annihilated and a single photon with exactly
half of the wavelength (dark blue) is emitted. No real energy level is
required for SHG. For TPA, the two photons are absorbed to a real energy
level. After nonradiative relaxation, a single photon with more than half of
the wavelength (light blue) is emitted.
P = ε 0  χ (1)E + χ (2)E 2 + χ (3)E 3 +  (9)
The lower order harmonic generation is the SHG. As shown
schematically in Figure  5, SHG can be described in a quantum
mechanical picture as the excitation of an atom to a virtual energy
level by the simultaneous annihilation of two coherent photons
with the same energy, instantaneously followed by the relaxa-
tion and emission of a frequency doubled photon. This quantum
mechanical picture does not require the excitation to the real state.
Consequently, SHG is not a resonant process and compared to
two-photon absorption and fluorescence, the SHG process occurs
instantaneously and has a narrower bandwidth than the excitation.
The probability that two photons are meeting simultaneous
in a material is extremely low for small driving electric field,
with a characteristic timescale higher than the age of the uni-
verse. It was only with the invention of the laser,[84] which gener-
ates coherent waves with high electric fields, that experimental
observation of SHG become possible.[85] In addition to high
electric field strengths, SHG is possible only in noncentrosym-
metric media. This requirement is reflected in the second order
susceptibility tensor χ(2), which has the same symmetry as the
medium. Only noncentrosymmetric media and materials have
a nonvanishing χ(2) components (Equation (10)).
The second order polarization vector P(2) is given by
Equation (10)
Pi(2) = ∑ε 0 χ ijk
( 2)
E j E k (10)
j ,k
E 2 = [E x2 E y2 E z2 2E yE z 2E xE z 2E xE y ]T . From the condition that
χ(2) ≈ χ(1)/Eatom, a first approximation of the χ(2) components of
1 pm V−1 is obtained.[83] Table 3 shows the measured values of
dij for BaTiO3 in comparison to other materials. The values of dij
have also been calculated by several models. One phenomeno-
logical approach is the “bond anharmonic polarizability model,”
which calculates the nonlinear polarization of the crystal as the
sum of the polarizations induced by each bond between the
atoms in the crystal.[87,88] Another phenomenological approach
calculates the second order susceptibility from the second order
term in field dependent bond polarizabilities.[89] According to
these models, the largest contribution to the second order sus-
ceptibility of BaTiO3 is given by the TiO bond, where the lack
of inversion symmetry of BaTiO3 also originates.
To overcome limitations of these models, which do not take
the bandgaps into account, more sophisticated first-principle
approaches which deduce the values of χ(2) from the band
structure of the material have also been developed.[94] While all
these models have a relatively good agreement with the experi-
mentally determined values, discrepancies are still present in
particular for the low-frequency values of χ(2). Furthermore, the
experimental determination of χ(2) is also challenging, which
leads to discrepancies between the experimental values as well.
The second order susceptibility of BaTiO3 is comparable to
the other metal oxides (Table 3), but BaTiO3 has the advantage
Table 3.  The linear and nonlinear optical properties of BaTiO3 and other
materials. Classification by crystal structure and symmetry class, energy
gap Eg, reduced second order susceptibility tensor elements dij and two-
photon absorption coefficient β2. The values were measured at the wave-
lengths given in parentheses.
Material Crystal Symmetry Eg [eV] dij [pm V−1] β2 Reference
structure [cm GW−1]
BaTiO3 Tetragonal P4mm 3.5 d33 = 6.8, 0.1 (596 nm) [90]
d31 = 15.7,
d15 = 17
@ 1064 nm
LiNbO3 Trigonal 3m 4.0 d33 = −34, 3.5 (388 nm) [90,91]
d31 = −4.9, 0.1 (514 nm)
d22 = 2.6
@ 1058 nm

where χ ijk are the tensor components of χ(2), a third rank tensor
(2)
KNbO3 Orthorombic Bmm2 3.95 d33 = −19.6, 0.032 [90,92]
d32 = 11.3, (846 nm)
with 27 components, and Ej,k are the driving electric field vector
d31 = −12.9
components. However, due to symmetry constraints, the values
@ 1064 nm
of χ ijk are not independent. First, if the SHG occurs at optical fre-
(2)

quencies below the resonant frequency of the material, the GaAs Cubic 1.42 d14 = 209.5 70 (1060 nm) [90,93]
4 3m
@ 1058 nm
second order susceptibility is frequency independent. Thus, in

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of extremely high EO coefficients. While GaAs and other semi-
conductors have high second order susceptibilities, their EO
coefficients are much lower (around 1.5 pm V−1) and further-
more have the disadvantage of being conductive when too high
electric fields are applied for EO switching. Thus, BaTiO3 offers
a convenient compromise for multifunctionality.
The SHG response depends strongly on the driving elec-
tric field polarization. For BaTiO3, the highest χ(2) component
is d15, thereby an electric field polarized along this direction
maximizes the SHG. Using the Voigt notation, d15 corresponds
to dxxz, which is not parallel to any BaTiO3 crystal axis. Thus,
the highest SHG from a BaTiO3 slab, illuminated by a nor-
mally incident p-polarized beam can be obtained when the
c-axis (assumed parallel to the z-axis) is in plane normal to the
incidence. Additionally, the incident laser intensity (W cm2) is
also an essential parameter for inducing a nonlinear response.
The SHG intensity scales with the square of the laser inten-
sity because SHG is a second order phenomenon. Also, the
focusing setting of the incident laser beam impacts the SHG
emission, with the strongest signal coming from the focus
point. Thus SHG can be used for confocal imaging.
In bulk crystals, phase matching is also required for efficient
SHG, in addition to the correct orientation of the oscillating
driving electric field. Phase matching conditions are necessary
due to the dispersion of the refractive index. SHG is emitted
quasi-instantaneously along the path of the incident wave.
Hence, the total SHG from a sample is the interference of SHG
from all the points in the path of the incident wave. Because
SHG propagates at a different velocity compared to the incident
wave, this superposition leads to a high total SHG only when
phase matching requirements are met and the incident and
SHG waves are in phase. Thus, the total SHG from a sample
depends strongly on the excitation wavelength and the length
of the sample. To obtain maximum SHG intensity, the phase-
matching condition Δk = 2k(ω) − k(2ω) = 0 between the exci-
tation and the emitted waves must be fulfilled. If this phase
matching condition is not satisfied, the total SHG is periodi-
cally cancelled along the sample due to destructive interference,
with a period inversely proportional to Δk. In case of nanostruc-
tures with sizes much smaller than the excitation wavelength,
the phase matching condition is relaxed.[83,95]
2.5.2. Two-Photon Fluorescence
Two-photon fluorescence appears after two photons with
the same energy are absorbed by a material, followed by the
emission of a single photon with lower energy. Although this
process also requires the quasi-simultaneous absorption of
two photons, it is fundamentally different than SHG, because
it requires the existence of a real high energy state to which
the atom is excited (Figure  5b). Thus, the probability of two-
photon absorption is very high for photons with energy higher
than the bandgap of the material. Furthermore, it also involves
the nonradiative decay from the high energy state to the fluo-
rescent excited state, before the fluorescent photon emission.
This nonradiative decay introduces a time delay before the
fluorescence occurs, making fluorescence photons incoherent,
as opposed to SHG. The rate of two-photon absorption rate
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is given by an extended Beer-Lambert expression dz dI = − αI − βI 2,
where α is the linear absorption coefficient. The two-photon
absorption coefficient β is proportional to the imaginary part
of χ(3),[96,97] which is not vanishing for centrosymmetric mate-
rials. Since two-photon fluorescence is not a coherent process,
phase matching conditions are not required. Fluorescence from
BaTiO3 after doping with transition metals, rare earth ions or
mixed with plasmonic metals demonstrates such response. The
optical properties of doped BaTiO3 are presented in Section 2.6.
2.5.3. Kerr Nonlinearity
The third order susceptibility tensor gives rise to another
important nonlinear effect, which is the intensity dependent
refractive index, also known as the Kerr nonlinearity. The
dependence of the refractive index on the intensity I is given by
n = n0 + n2I (12)
where n2 is known as the nonlinear refractive index and is
related directly to χ(3) by n2 = 12π 2 χ (3) /n02 .
2.5.4. Nonlinear Response at the Nanoscale—The “Size” Effect
BaTiO3 has been successfully fabricated in nanoparticle and
nanolayers form. Both these structures can be formed of
BaTiO3 grains with sizes as small as 20 nm. Thus, it is relevant
to understand how the nonlinear response changes in these
dimensions. As the nonlinear optical properties stem primarily
from the crystal structure, understanding how the crystal struc-
ture is affected at the nanoscale already gives valuable indica-
tions about the nonlinear optical conversion efficiencies.
First, the characteristic size of BaTiO3 nanostructures is much
smaller than the coherence length of the material, which is typi-
cally a few micrometers. Thus, fulfilling the phase-matching con-
dition is not an issue at this size scale. Therefore, in composite
geometries, phase-matching conditions are relaxed, also named
random quasi-phase matching. Experiments have reported
random quasi-phase-matching in polycrystalline ferroelectrics and
in complex assemblies of BTO nanoparticles.[98] In comparison to
phase matching in single crystals, where the SHG intensity oscil-
lates along the sample, in composites with random quasi-phase
matching, such as disordered polycrystals, show a linear growth
of the intensity with the thickness of the material and a broad-
band acceptance bandwidth. For sample with nanoscale size,
the second order conversion efficiency can still depend on the
wavelength when χ(2) has a wavelength dependence, for instance
near the bandgap, or when optical resonances occurs.
Next, the SHG does not exclusively appear from materials
with noncentrosymmetric crystal structure. At the nanoscale
the shape of the nanostructure breaks the inversion symmetry,
thus SHG appears due to the surface of the nanostructure and
if it has an asymmetric geometrical shape. Thus, SHG has
been successfully detected in nanostructures such as nanopar-
ticles and thin layers from centrosymmetric materials such as
metal,[99] where the presence of hotspots near the surface leads
to strong SHG conversion efficiencies.
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However, for dielectric nanostructures, SHG is more efficient
if the crystal structure is noncentrosymmetric. Consequently,
the behavior of the second order susceptibility χ(2) as sizes go to
the nanoscale has been addressed in several works. Theoretical
studies predict that ferroelectricity, which is linked to the pres-
ence of SHG, is present locally in colloidal quantum dot sized
(below 5  nm) BaTiO3 nanoparticle under zero field.[100] This is
confirmed in ensemble studies of concentrated nanoparticle
solutions,[101,102] powders of ball milled nanoparticles,[103] but also
on measurements performed on single nanoparticles.[101,104,105]
Kim et  al.[105] demonstrated that the SHG polar measurements
from single BaTiO3 nanoparticles have a characteristic dipolar
and quadrupolar shapes which is typical of bulk down to diame­
ters of 30 nm. Several models are proposed to explain this tran-
sition. Two of these models prescribe that the ferroelectricity
of the BaTiO3 nanoparticle is reduced due to the size, either
because the ferroelectricity decreases strongly with the volume
or because the surface effects overcome the bulk emission.[106–108]
Other observation indicates that the presence of ferroelectricity
at BaTiO3 nanoparticles smaller than 30 nm depends on using a
fabrication method which results in strain at the nanocrystal sur-
face.[103] The third model suggests that the BaTiO3 nanoparticles
are composed from a core with tetragonal crystal structure and
a cubic or disordered shell region.[109] The thickness of the shell
is hypothesized to be independent of the nanoparticle diameter,
because it appear due to crystal relaxation as the nanoparticle
surface. Thus, as the nanoparticle diameter decreases below a
certain threshold, the optical properties of the shell overcome the
core’s. However, for BaTiO3 nanoparticles bigger than 100 nm, a
study of the polarization SHG maps from single nanoparticles
shows the contribution of the core to the total SHG signal is sig-
nificantly higher compared to the surface contribution.[110] A sim-
ilar model is suggested for BaTiO3 ceramic composites, where
the ferroelectric behavior is consistent with the presence of fer-
roelectric grains and nonferroelectric grain boundaries, which
have a higher volume fraction as the grain size decreases.[111]
Another work compares the SHG from BaTiO3 nanoparticles
which claim cubic and tetragonal crystal structures from com-
mercial sources and synthesized in-house.[112] SHG was detected
from all these nanoparticles, but STEM EELS measurements
show variations of the crystal structure from each type. This vari-
ation indicates the presence of tetragonal and cubic phases with
different ratios in the core of the nanoparticles and also hints
to the presence of surface reconstruction. These studies indicate
that at least a core with tetragonal crystal structure is present in
BaTiO3 nanoparticles and the second order susceptibility values
are very similar to the bulk values.
In addition to SHG, BaTiO3 nanoparticles are also an effi-
cient source of higher harmonic generation. Measurements on
BaTiO3 in nanoparticles in glycol solution show that the non-
linear refractive index, which is associated with the third order
susceptibility, is enhanced by four orders of magnitude in com-
parison to the bulk and normalized by the volume.[113]
2.5.5. Tunable Nonlinear Optical Properties of BaTiO3
Nanoparticles and Nanowires (NWs)
The optical properties of BaTiO3, in particular the first order
and third order susceptibilities, which is related to the nonlinear
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refractive index and two-photon absorption, can be modified by
combining BaTiO3 with metals to obtain composite layers,[114–118]
or by coating BaTiO3 nanoparticles with metallic seeds.[119]
The insertion of noble metals to BaTiO3 creates BaTiO3–metal
composites, where the Kerr nonlinearity is increased by the
plasmonic resonance of metals which effectively enhances the
electric field locally.[114,120–122]
As BaTiO3 is a bandgap insulator, photoluminescence
(PL) was detected at excitation wavelengths within the energy
bandgap ≈3.2 eV from BaTiO3 nanoparticles with sizes between
80 and 100 nm. The nanoparticle size red shifts the maximum
of PL intensity red shifts, which consists of contributions from
the surface states, where the crystal structure is distorted, and
from self-trapped excitons.[123] It is possible to obtain photo­
luminescence with excitation wavelengths outside the bandgap
by doping with oxygen vacancies, which leads to the additional
formation of self-trapped excitons.[124] Visible photoluminescence
is also achieve using highly disordered states obtained with Mn
doping[125] or in hollow nanofibers.[125]
The SHG conversion efficiency of BaTiO3 can also be opti-
mized. For BaTiO3 films, in which the c-axis of the constituting
grains is not oriented in the same direction, periodic poling
applied close to the Curie temperature improve the SHG con-
version efficiency by reorienting the grains in the same direc-
tion.[55] A modification of the actual value of the second order
susceptibility is achieved when the first order susceptibility is
modified, as the two quantities are connected by the Miller’s
rule.[126] Doping can increase of the first order linear suscep-
tibility, leading to a half of an order of magnitude increase of
the second order susceptibility.[127] One order of magnitude
increase of the second order susceptibility was obtained by
combining doping with stress by growing BaTiO3 layers on
lattice mismatched substrate such as SrTiO3.[128] The combina-
tion of stress and Ce doping leads to an improvement of the c/a
ratio, which modifies the value of χ(2) strongly.
Combining BaTiO3 with plasmonic materials, in particular at
the nanoscale,[129,130] leads to an improved SHG conversion effi-
ciency. However this is due to the plasmonic resonance of the
metallic nanoparticles and does not change the χ(2) of BaTiO3.
The same principle of exploiting a resonance to improve the
second order conversion efficiency is employed in BaTiO3 nano­
particles with Mie resonances,[131,132] where the SHG conversion
efficiency normalized by the volume is two to three orders of
magnitude higher in comparison to layers or bulk BaTiO3.[95]
2.6. Doping Effect in BaTiO3
The doping of BaTiO3 with several chemical elements is pos-
sible, therefore offers unique opportunities to engineer the
properties of the crystal in a range of applications. BaTiO3 upon
doping may modify properties such as: Curie temperature,
electric permittivity, grain size as well as the refractive index,
the electrooptic response and obtain light emission proper-
ties.[133–135] Both acceptor and donor-type additions in BaTiO3
have an impact on the quality of the crystal and the related
properties. Here, we will review the materials used to improve
photonic properties of BaTiO3 thin films.
Whether a dopant ion is compatible with the host medium is
dependent on parameters like the site type, the compensation
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mechanism and the solid solubility limit.[136] Crystals
with ABO3 structure (with Ba on the A site and Ti on the
B site for BaTiO3) accept two types of dopants. The Ba2+ posi-
tions can be substituted by ions of large ionic radii of valence3+
and higher, while the Ti4+ sublattice are compatible dopant ions
with smaller ionic radii of valence 5+ and higher.[153,154] The
three-valent ions can substitute either the A-type or the B-type
sites, where the ions substitute the Ba2+ sites act as donors,
while the Ti4+ sites act as acceptors (e.g., Mn, Fe, Ni, or Cr).
For the doping with rare earth ions, the BaTiO3 defect chem-
istry mainly depends on the lattice site where the ion is sub-
stituted.[155] All rare earth 3+ elements are larger than Ti4+ and
smaller than Ba2+. Therefore, the doping of BaTiO3 with rare
earths, result in the expansion of the lattice on the B-site and
the shrinkage on the A-site. During doping, BaTiO3 may turn
into semiconducting or metallic state, however this is not yet
clear if it is dependent solely on the doping effect or the modi-
fication induced in crystal such as the grain size or oxygen
reduction during the doping process.[156] The modification
over the grain size mainly relies on the ionic radii mismatch
between the substituting and parent atoms. If the ionic radius
of the doped atom is larger than that of the parent atom grain
size becomes larger and vice versa.[144]
We can recognize three main modifications in properties of
BaTiO3 after doping such as: bandgap/refractive index modifi-
cation, enhancement of second or third order nonlinear optical
properties, and photoluminescent response. In Table  4 is pre-
sented a list of dopants together with several properties accom-
panied with each doping element.
Fasasi et  al. prepared barium titanate thin films doped
with zinc oxide (ZnO),[141] tungsten oxide (WO),[152] and gado-
linium (Gd)[151] by pulsed laser ablation. They tested various
doping concentrations. The films doped with ZnO and Gd
remain tetragonal, while for WO samples remain cubic even
after postannealing. The transmittance of the aforementioned
doped films was strongly affected by postannealing conditions.
The bandgap energy was modified by film thickness and the
amount of dopant added. They suggested that Gd in BaTiO3
modifies chemical properties of the films and generates a tran-
sition with bandgap energy of 4.35 eV.
Transition metals such as chromium (Cr) was studied by Eden
et al.[138] They have managed to replace titanium ions with chro-
mium and have recorded the blue-shift in the bandgap energy, as
well as a photoluminescence response in near-infrared. The Cr
doping resulted in larger absorption over the visible region and
three absorption bands at about 470, 575, and 610 nm. However,
after cooling the sample at −200  °C and exposed to a 400  nm
laser, four sharp lines appeared in the near infrared and several
additional weak emission lines. An important metal for doping
BaTiO3 is erbium, since Er3+ ions have optical fluorescent proper-
ties particularly useful in laser applications.[146–149] The work from
Block and Wessels[146] reported on Er-doped BaTiO3 thin films.
The strong Er3+ intra-4f shell emission at 1550 nm was recorded
at −257 and 21  °C, with linear dependence of the Er3+ lumines-
cence intensity to the pump power and lifetimes of 8 ms.  The
OH complexes play a crucial role, as luminescence quenching
centers weaken the emission from the excited Er ions.[147] Zhang
et  al. used the sol–gel method to produce Er-doped BaTiO3
crystalline films.[148] Optical pumping at 514 and 980  nm wave-
lengths, led to strong photoluminescence signal at telecom band.
Transient photoluminescence measurement showed that con-
centration quenching occurs when the concentration of Er is
>3.0 mol% with a lifetime of the order of few msec.
Another rare earth ion dopant that has been extensively
studied on the optoelectronic response of BaTiO3 is cerium (Ce).
Xuan et al. studied the impact of Ce doping on BaTiO3.[127] Thin
films produced by pulsed laser deposition and show a tenfold
enhancement on the SHG signal produced by 1064  nm light
illumination. This enhancement was explained by two factors,
first the linear susceptibility of doped films is 1.43 times larger
than undoped films, and second the lattice parameter ratio
c/a increases and spontaneous polarization in the direction
of c-axis, and hence d33 has the largest enhancement. Further-
more, Liu et  al.[145] reported on the impact of cerium over the
electrooptic response of Ce-doped BaTiO3. Upon doping BaTiO3
with cerium the lattice constants are increased, because the Ce4+
has larger radius than the Ti4+. Thereby, authors deduced that
the cerium substitutes titanium, which result in larger spon-
taneous polarization, as well as lattice distortion. According to
Didomenico and Wemple’s model[52] the electrooptic response is
proportional to the product of the spontaneous polarization and
the dielectric constant. Therefore, the electrooptic coefficients of
BaTiO3:Ce are 1.5 times larger than the undoped BaTiO3 crystal.
The thin films they produced by PLD method, possess an elec-
trooptic coefficient of 80 pm V−1 for Ce-doped BaTiO3 films and
50 pm V−1 for undoped BaTiO3 films.

Table 4.  Doping elements for BaTiO3 modification. A list of the chemical elements used to dope BaTiO3, the growth method, the substitution site of
the ABO3 form, the phase of the produced crystals, and the photonic applications that are used.

Dopant Growth method A/B site Phase Application Reference

Cr Solid state B Hexagonal, tetragonal Bandgap mod. and photoluminescence [137,138]
Fe Sol–gel/PLD B Tetragonal, amorphous Kerr nonlinearity [115,139]
Co PLD B – Bandgap mod. [140]
Zn PLD B Tetragonal Bandgap mod. and refractive index [141]
Rh PLD – Tetragonal Kerr nonlinearity [142]
Ce PLD B – SHG, Kerr nonlinearity, EO effect [127,143–145]
Er MOCVD, RF sputtering, sol–gel A or B Tetragonal Photoluminescence [146–150]
Gd PLD A – Bandgap and refractive index [151]
W PLD A – Bandgap and refractive index [152]

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Furthermore, doping with transition metals like iron or

noble metals (such as silver, gold, and rhodium) have led to
enhanced optical nonlinearities. Using standard z-scan meas-
urements, the real and imaginary parts of the third-order
nonlinear susceptibility for rhodium doped BaTiO3 χ(3) were
7.98  × 10−15 m2 V−2 and 13.4  × 10−16 m2 V−2,[142] while for the
iron doped BaTIO3 the real and imaginary parts of the third-
order nonlinear susceptibility χ(3) were determined to be
10.04 × 10−15 m2 V−2 and −12.02 × 10−16 m2 V−2, respectively.[115]

2.7. THz Properties of BaTiO3

The fundamental understanding and precise interpretation of

the intrinsic dielectric behavior of BaTiO3 are essential for the
design and optimal operation of devices in the THz regime.
The dielectric response to infrared waves polarized along or
transverse to the tetragonal axis of BaTiO3 has been a field to
study the nature of certain structural phase transitions. Fourier
transform-IR spectra of films and of bulk crystals at mid-IR
show that BaTiO3 remains transparent in the same levels as in
the near-infrared up to the wavelength of 14 µm (≈700 cm−1),[157]
which corresponds to the first longitudinal optical mode (Axe
mode).[158,159] For shorter wavelengths, depending on the quality
of the crystal and the preparation method OH− absorption peaks
may occur at ≈2.85 µm (3500 cm−1) and ≈6.7 µm (≈1500 cm−1),
while C-H double absorption peak may exist at ≈3.4  µm
(2935 cm−1).[160] For longer wavelengths in the far-infrared
regime (30–700 cm−1) the dielectric responses are obtained by
means of Fourier transform scanning interferometry,[158,161]
time-domain THz spectroscopy[162,163] or even infrared spec-
troscopic ellipsometry.[159] Further resonant modes related to
lattice vibrations called the Slater, Last, Axe, and O4 torsional
modes are all infrared-active phonons and can be also identi-
fied by Raman spectroscopy.[164] On Figure  6a is presented the
reflectivity spectrum of a bulk tetragonal BaTiO3 crystal at room
temperature, as reported by Servoin et al.[158] The real and imag-
inary part of dielectric constant at 25 and 128  °C for a single
crystal with thickness of 120 µm is presented in Figure 6b,c as
reported by Hlinka et al.[165]
The applications of BaTiO3 in THz and far-infrared spectrum
extend over: THz generation and electrooptic sampling,[166,167] for
the synthesis of index matching solutions,[168] the construction
of complex nanocomposites[169,170] and photonic crystals.[171,172]
3. BaTiO3 EO Thin Films
Here, we present the EO modulators developed based on
BaTiO3 films and categorize them over the growth method
employed. The thin film technology has been an enabling plat-
form to replace bulk crystals for electrooptics. Properties of the
produced films like surface roughness, extrinsic or intrinsic
defects, domain size and grain boundaries of the crystal is of
paramount importance for the operation of the EO photonic
waveguides. Therefore, all these factors can add up to the total
optical losses of the thin film devices and compromise per-
formance. Methods related to epitaxial growth via molecular
beam epitaxy, wafer bonding and smart cut technologies have
Figure 6.  Far-infrared and THz dielectric properties of BaTiO3. a) Reflec-
tivity spectrum of bulk single crystal, for polarized fields along a-(red)
and c-(black) axis, at room temperature. Data collected from ref. [158].
b,c) Real and imaginary part of dielectric constant, respectively over THz
range for a tetragonal crystal. Plots are measured for room temperature
(black) and above Curie temperature (blue), as indicated. Data collected
from ref. [165].
allowed large-scale fabrication of thin films and their transfer
to another substrate. From the manufacturing point of view, the
large-scale uniformity is equally important to the contraction of
production costs. Thus, fabrication methods with low-cost and
large-scale uniformity of thin films are of great importance.
The underlying physical mechanisms related to functionalities
like electrooptic modulation or harmonic generation are highly
dependent on the phase of the crystal structure, as it was pre-
sented in part 2.
3.1. PLD and MOCVD Grown BaTiO3 EO Films
The first experimental work reporting on the EO response
from BaTiO3 thin films was published by Gill et  al.[173] They
demonstrated a channel waveguide, fabricated by low pres-
sure CVD deposition of BaTiO3 on MgO substrate followed
by standard photolithography to fabricate the waveguides. The
waveguides were constructed in a 320  nm thick BaTiO3 film,
with a surface roughness of 13  nm and after mechanical pla-
narization surface roughness was reduced to 5  nm. Authors
claimed that planarization process improved the quality of
the waveguides and reduced the surface scattering losses.
Employing wet etching methods, they managed to build wave-
guide ridges.
The electrooptic response of the waveguide characterized for
near-infrared light of 1.5 µm wavelength and linearly polarized
at 45° to the vertical. Modulation of the signal was achieved by
placing a polarizer at the output of the waveguide and applying

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Figure 7.  Electrooptic waveguides and plasmonic interferometers made from PLD and MOCVD BaTiO3 films. a) Schematic of the Mach–Zehnder
waveguide modulator, (oblique view and cross-section). b) Modulation depth (for a BaTiO3 crystalline film with the c-axis out of plane) versus frequency
(21 Vpp modulating square signal, 46 Vdc bias, 1550 nm). (a,b) Reproduced with permission.[174] Copyright 2002, AIP Publishing. c) Cross-sectional SEM
image of a polycrystalline film and d) AFM image of 1 µm thick polycrystalline BaTiO3 film on MgO, with a maximum height variation of 6.3 nm. The
rms roughness for the measured area is 0.9 nm. (c,d) Reproduced with permission.[175] Copyright 2003, The Optical Society. e) Schematic of a plasmonic
modulator based on interference of SPPs launched from a set of parallel slits milled into a planar silver film. The counter-propagating SPPs travel
along the Ag/BaTiO3 interface. The interference of these SPPs with the transmitted fields can be controlled by an applied voltage across the BaTiO3
layer, by means of EO modulation or domain switching. f) CCD image of a double-slit SPP interferometer array. Insets: Scanning electron micrograph
of slit pairs milled by focused ion beam in a chromium on silver layer. 50× image of devices with slit pitches varying from 1.5 to 1.98 µm showing the
transmitted intensity oscillation. (e,f) Reproduced with permission.[178] Copyright 2008, American Chemical Society.

either a dc or dc + ac voltage across the device electrodes. Films
had an effective dc electrooptic coefficient of reff = 50 ± 5 pm V−1
and reff = 18 ± 2 pm V−1 at 5 MHz. The reported EO coefficient
is weaker by more than one order of magnitude in comparison
to the EO response of bulk BaTiO3.
Petraru et  al.[174] produced BaTiO3 films via pulsed laser
deposition on MgO substrates. They made Mach–Zehnder
optical waveguide EO modulators and tested how EO response
changes for films with the c-axis oriented either in-plane or
out-of-plane. They produced films of different orientation
by adjusting the energy of laser pulses of the PLD process
to either 1100 or 300 mJ pulse−1. The waveguides were of the
ridge type, with the BaTiO3 thickness to be 1 µm, the ridge step
50  nm, and the width 2  µm. The BaTiO3 waveguide propaga-
tion losses were 2–3 dB cm−1. Electrodes of 3 mm length were
deposited on each side of the waveguides. EO modulation has
been demonstrated with Vπ = 6.3 V at 632 nm wavelength and
Vπ  = 9.5  V at 1550  nm wavelength for the samples with the
c-axis in-plane. For the c-axis oriented out-of-plane, they found
a Vπ of 8 V at 632 nm wavelength and a Vπ of 15 V at 1550 nm.
The typical bias dc voltage ranges from 50–60 V. It was shown
that by increasing the dc bias, the EO coefficient also increased
due to the poling of the films, however an upper limit is set by
the leakage current of the films. The theoretical estimations of
the EO modulators suggest a Pockels coefficients r51 = 80 pm V−1
for the films, where the c-axis was out-of-plane and an effec-
tive Pockels coefficient reff = 734 pm V−1 for the films where the
c-axis was in-plane. The EO modulation was characterized up
to 1  MHz modulation speed, where no considerable reduction
of the modulation depth was recorded. The schematic of such
devices and the measured modulation depth versus frequency
at 1550 nm is shown in Figure 7a,b.
In a follow up letter from the same group,[175] polycrystalline
films of BaTiO3 were tested. Films of ≈1  µm thickness were
grown by PLD, similar to previous reports, however the depo-
sition temperature was ≈400  °C. They characterized the films
with a prism-coupling technique and deduce the in-plane and
out-of-plane refractive indices, nTE  = 2.316 and nTM  = 2.301 of
the polycrystalline films at 633 nm. The films were birefrin-
gent, with a birefringence of 0.015 ± 0.002. The cross-sectional
scanning electron microscopy (SEM) image (Figure  7d) of
the film shows a dense structure without a columnar aspect,
thereby the relatively high birefringence was attributed to a
preferential orientation of the crystallites. They also observed
that the modulator exhibited hysteretic behavior when they
measured the output intensity versus the applied voltage; i.e.,
the scan with the voltage going up was shifted with respect to
the scan with the voltage going down. This indicates a ferroe-
lectric poling effect of the BaTiO3 during the measurements. In
the same configuration of a Mach-Zehnder interferometer, the

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EO coefficient at the 1.5 µm wavelength was measured ≈22 pm bias. Since the intensity modulation data recorded for each
V−1. A square-wave voltage was applied to the modulator, and a device did not undergo the same change in nSPP, authors specu-
stable modulation in the frequency range of 1 Hz to 1 MHz was late that some change in index of this magnitude may appear
recorded. The measured half-wave voltage of the polycrystalline due to a-domain to c-domain switching in the active barium
EO modulator waveguides was Vπ ≈ 19 V at an applied electric titanate layer.
field of 9 V µm−1.
Later on, Tang et  al.[176,177] on back-to-back publications
studied the EO response of polydomain films of BaTiO3. They 3.2. MBE Grown BaTiO3 EO Films
produced films of 570  nm thickness by MOCVD. The poly­
domain texture corresponded to films with the c-axis oriented While MOCVD and PLD where the main fabrication methods
parallel and antiparallel of three main axis: <100>, <010>, to implement EO modulators based on BaTiO3 thin films in 90s
and <001>. The ferroelectric domains had dimensions of and 2000s, Abel et al. produced EO films out of molecular beam
50–500 nm, which was many times smaller than the operating epitaxial methods for first time.[179] They developed the direct
wavelength of 1542  nm. Authors assumed that some kind of growth of ferroelectric BaTiO3 films on silicon with EO coeffi-
averaging over several domains happened. In order to support cient of reff = 148 pm V−1. A year later, it was published the work
their hypothesis, they measured the bireference of the films by Xiong et al.[38] (Figure 8) where they also prepared via MBE
and the extracted values were lower than Δn  < 0.005 for most thin films of BaTiO3 with EO coefficient of reff = 213 ± 49 pm V−1.
films, an order of magnitude smaller than bulk crystals. The The improvement on the EO coefficient from previous work,
EO modulators were based on a single mode strip-loaded wave- lies on the integration of the films in resonant waveguide
guide design. The waveguide was 4 µm wide and 125 nm thick, geometries (namely micro-racetrack optical resonators and
fabricated using standard plasma enhanced chemical vapor MZI waveguides). The false colored SEM image in Figure  8a
deposition and reactive ion etching processes. The coplanar shows the developed waveguides. A horizontal slot waveguide
electrodes had length and separation distance of 3.2  mm and is made after sandwiching the BaTiO3 in between two silicon
8  µm, respectively. The waveguide was aligned to the <110> layers, Figure 8b. In such configuration, the optical mode over-
crystallographic direction of the MgO substrate, with wave- laps with the BaTiO3 film. They produced an 80 nm BaTiO3
guide propagation losses (≈1 dB cm−1). The dc bias dependence film with MBE on silicon-on-insulator (SOI) substrate, where
of the effective ΕΟ coefficient increased from a zero-bias value
of 141 pm V−1 to a maximum of 162 pm V−1 at a bias of 10  V.
Upon stronger biasing fields, the EO response was decreasing.
The reorientation of ferroelectric domains is the responsible
mechanism for the bias dependence. Domains with polariza-
tion normal to the film plane rotate 90° into the film plane if
the total electric fields exceed the coercive field required for
such motion. The change in birefringence due to 90° domain
switching contributes to the effective electrooptic coefficient,
and is rapidly reversible due to strong elastic interaction with
the substrate. For zero dc bias, the authors could not excite
domain switching (below the coercive field, Ec  < 1.6 MV m−1).
Further characterization at GHz frequencies of the EO modula-
tors shows a Vπ of 3.9 at a 2.0  V dc bias. The −3  dB electrical
bandwidth measured to be 3.7 GHz and the effective EO coef-
ficient calculated as 150 pm V−1 at 1561 nm wavelength.
Dicken et al. prepared thin films of BaTiO3 via PLD, to elec-
trically control the surface plasmon polariton (SPP) wavevector
(k-SPP) of a metal-dielectric plasmonic interferometer.[178] They
fabricated arrays of subwavelength interferometers from pairs
of parallel slits of silver on top of BaTiO3 thin films. Plasmon-
mediated transmission of incident light through the subwave-
length slits was modulated by an external voltage applied across
the barium titanate thin film, see Figure  7e,f. TM polarized Figure 8.  Electrooptic waveguide modulators based on MBE grown films
laser light at 688  nm illuminated the array of nanoslits. The of BaTiO3. a) False-color scanning electron micrograph of an amorphous
slits pitch started at half micrometer and increases by 20  nm silicon waveguide (in blue) and the gold electrodes (in yellow). b) High-
for each device along a row. The observed intensity oscilla- resolution transmission electron micrograph of a cross sectional area of
tion as a function of slit pitch is due to SPP interference with the a-Si/BaTiO3/Si. c) Normalized electrooptic response (|S21|) in dB, as
light transmitted through each slit. Transmitted light modula- a function of the modulating frequency in logarithmic scale. The −3 dB
electrooptic bandwidths for the Mach−Zehnder interferometer (MZI) and
tion was ascribed to two effects, electrically induced domain
the racetrack resonator are 800 MHz and 4.9 GHz, respectively. Inset: a
switching and electrooptic modulation of the barium titanate 300 Mb s−1 nonreturn-to-zero eyeline diagram measured on the MZI mod-
index. Devices in the pitch range of 2.52–2.80  µm showed an ulator. SOI horizontal slot waveguide. Reproduced with permission.[38]
EO change in the SPP index of ΔnSPP  = 0.001 at 45  V applied Copyright 2014, American Chemical Society.

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an intermediate layer of strontium titanate (STO) was used.

Using this geometry, they created lightwave circuits on BaTiO3-
on-silicon substrates, including nanophotonic components,
such as micro-ring resonators and optical interferometers. The
waveguides were lithographically patterned on amorphous sil-
icon layer, circumventing the challenge of dry etching BaTiO3.
The poling of the ferroelectric domains in these epitaxial films
was necessary to improve EO response of the films, since films
produced had four in-plane tetragonal orientations parallel and
antiparallel to <100>, <010> directions. Poling of BaTiO3 was
realized after applying an electric field along one arm of the
BaTiO3 MZI device, where the length of the modulating arm
was LMZI = 400 µm, and the spacing between the two electrodes
was 10  µm, with a peak-to-peak amplitude of 20  V at a fre-
quency of 10 Hz. The EO effect was measured at 1543.5 nm, on
a longer MZI waveguide with an arm length of 750 µm. The Vπ
was 20 V, leading to a voltage length product of VπL = 1.5 V·cm
at a frequency of 1  MHz, for a dc bias Vbias  =  +20  V. Authors
characterize the EO response up to 4.9 GHz (Figure 8c).
Recently, Abel et  al.[39] reported on the highest EO coeffi-
cient ever recorded on a noncentrosymmetric thin film. They
developed a fabrication process to allow BaTiO3 to be integrated Figure 9.  BaTiO3 nanoparticles for biophotonics. a) HeLa cells coated
with nanoscale silicon photonic devices. They grew epitaxially with BaTiO3 nanoparticles. Left: wide field image. Right: 3D two-photon
a single-crystalline BaTiO3 on a silicon substrate. Then, a 5 to photothermal microscope image obtained from axial sections at 2  µm
intervals. Reproduced under the terms of a Creative Commons Attribu-
10 nm thick Al2O3 layer was deposited on the BaTiO3 layer in
tion CC-BY license.[97] Copyright 2017, The Authors, published by Springer
order to bond the BaTiO3 and another silicon wafer covered Nature. b) Overlap between the transmission image and the SHG image
with SiO2. Using these multilayers, optical waveguides and (green signal) of HeLa cells labelled with SHRIMPS. Reproduced with
plasmonic phase modulators were fabricated supporting data permission.[186] Copyright 2010, Elsevier. c) In vivo image with SHRIMPS:
modulation up to tens of GHz. The experimentally measured scanning confocal imaging of two BaTiO3 nanoparticles embedded at a
Pockels coefficients were found r42  = 923 ± 215 pm V−1 and depth 100 µm in a mouse tail tissue. The depth is along the z-axis. Repro-
duced with permission.[181] Copyright 2011, The Optical Society.
r33 = 342 ± 93 pm V−1. The racetrack resonators had various ori-
ented straight sections relative to the crystal axes and supported
transverse electric (TE), as well as transverse magnetic (TM) increased in the visible, so this technique has the potential to
polarizations with 39% or 55% of the optical power confined work with light further in the infrared spectrum.
in the BaTiO3 layer, respectively. Electrodes separation distance The multi-photon luminescence of BaTiO3 nanofibers can also
was 4 µm. The TE photonic waveguides demonstrate a low VπL be tuned by thermal annealing and doping. BaTiO3 nanofibers
product less than −0.5 V cm, which is similar with other state- produced by electro-spinning usually have an amorphous crystal
of-the-art integrated Si and InP EO phase shifters. structure when annealed to temperatures up to 500  °C. These
nanofibers have localized states in the bandgap due to disorder
that contribute to an intense photoluminescence in the visible.
4. Photonic Applications of Barium Titanate The BaTiO3 nanofibers gain an ordered tetragonal crystal struc-
ture by the introduction of Mn dopants or annealing at higher
Nanostructures
temperatures of up to 950 °C, which leads to a reduction of the
4.1. Nanoparticles and Nanowires photoluminescence in the visible, caused by Ba defects.[125,180]

4.1.1. Nonlinear Absorption and Photoluminescence

BaTiO3 nanoparticles have been considered as probes for
imaging due to their nonlinear optical properties. Most of the
energy absorbed in the two-photon absorption process is trans-
formed in nonradiative heat because BaTiO3 is a weakly fluo-
rescent material. This property of BaTiO3 nanoparticles is used
to develop high resolution bioimaging techniques with no fluo-
rescent materials. One such example based on the two-photon
absorption is two-photon photothermal microscopy, Figure  9a.
This pump–probe technique uses excitation in the near-
infrared, where tissues have low absorption, and its inherently
confocal.[97] Moreover, as shown in Section 2.5, the two-photon
absorption cross-section of the BaTiO3 nanoparticles can be
4.1.2. Harmonic Generation
BaTiO3 nanoparticles, as part of the more general category of
harmonic nanoparticles (HNP), are a promising candidate as
markers for bioimaging.[181–183] In comparison to quantum dots
or molecular dyes, the SHG signal from harmonic nanopar-
ticles is nonblinking and nonbleaching. SHG has a narrower
bandwidth that the excitation, which allows for excellent sepa-
ration between the excitation and emission. Furthermore, the
excitation of the HNP can be achieved with infrared light, which
penetrates tissues to deeper levels. The excitation of HNPs
requires the use of an ultrafast laser, with typical pulse duration
<100  fs, which increases the cost of this technique. However,

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diode-pump mode-locked Ti:Sapphire lasers with significantly

more affordable price, have recently become available.
In the case of BaTiO3 nanoparticles above a certain size (usu-
ally more than 80 nm), the values of the χ(2) components appear
to be very similar to the bulk values. This was verified by hyper-
Rayleigh scattering (HRS) measurements, which determine the
SHG from dilute colloidal suspensions of BaTiO3 nanoparticles.
This method suggests that the second order susceptibility is
very similar to the one of bulk BaTiO3 after accounting the size
of the nanoparticles. Generally, HRS gives smaller values of
the second order susceptibility compared to the bulk, but these
results are affected by the lack of monodisperse and agglomera-
tion-free colloidal suspensions.[102]
Several works indicate that BaTiO3 nanoparticles have very
low toxicity and are highly biocompatible,[184,185] showing no cell
damage after several hours. The BaTiO3 nanoparticles can be
introduced into living cells by endocytosis,[102] when the cells
are incubated in a nanoparticle solution.
BaTiO3 nanoparticles are proposed as second-harmonic radi-
ation imaging probes (SHRIMPs) to obtain additional imaging
data from cell. They offer a coherent signal and the possibility
to get deep tissue images. SHRIMPs can be employed for in
vitro[186] (Figure 9b) and in vivo[181] (Figure 9c) imaging and offer
high signal-to-ratio down to 50 and 120 µm depths, respectively,
even when endogenous SHG from the tissue is present.
In comparison to fluorescent biomarkers, SHRIMPs emit a
coherent signal that also depends on the size and on the orien-
tation of the HNP (Figure 10), as well as the polarization of the Figure 10.  SHG properties of nanostructured BaTiO3. a) Scattering cross-
incident beam (Figure 9b). By tuning the size of the SHRIMP, section (black line) and SHG (red dots) from a single BaTiO3 nanoparticle
the SHG can be maximized at wavelengths corresponding to (inset) showing a pronounced enhancement of the SHG when the scat-
tering has a resonance. Reproduced with permission.[95] Copyright 2017,
the scattering resonances of the HNP.[95] Furthermore, the
American Chemical Society. b) SHG polar response of a single BaTiO3
polarization dependence can be used to track the cells position nanoparticle. The black dots show the SHG measured for different polari-
and orientation for long periods of time.[187] zations of the incident beam. The red line is a numerical fit. Reproduced
A possible future application of BaTiO3 nanoparticles is in with permission.[187] Copyright 2010, The Optical Society. c) Optical setup
nanomedicine. As mentioned above, BaTiO3 nanoparticles used for harmonic holography (H2) measurement. The SHG signal from
have excellent biocompatibility, can be inserted, or attached to the sample S and the SHG from a reference of BBO are overlapped to
cells using biolabeling and have efficient SHG emission. Thus, record a digital hologram on the EMCCD camera. Reproduced with per-
mission.[189] Copyright 2009, The Optical Society. d) Using a SHRIMP to
BaTiO3 nanoparticles are strong candidates for theranostics, image a target located near a diffusive medium. The SHG from a single
acting as transducers to UV light that can to be used for photoac- SHRIMP placed passes through the diffuser. A digital harmonic hologram
tivation and generation of free radicals. The requirement of using of this signal is collected. Then the hologram is used to generate a beam
ultrashort pulses is of advantage, because this ensures reduced with the SHG wavelength and the same phase profile as the SHG signal,
secondary effects and activation by stray environmental light.[185] which is send back through the diffuser to the target, where it arrives as
Besides bioimaging and nanomedicine, BaTiO3 nanoparti- a focused beam. This focused beam is scanned over the target to obtain
its image. Reproduced with permission.[190] Copyright 2010, The Optical
cles have additional applications in photonics. Coherent spa-
Society. e) Improvement of the SHG spectra using MIIPS with a BaTiO3
tial microscopy was successfully employed to determine the nanoparticle to compress a pulse laser beam. Reproduced with permis-
position and the reduced second order susceptibility tensor of sion under the terms of a CC-BY-NC-SA license.[191] Copyright 2014, The
single BaTiO3 nanoparticles.[104] The polar response of the SHG Authors, published by Springer Nature.
can also be used to retrieve information about the crystal ori-
entation and modifications. The change of the SHG polar plot medium (Figure  10d), where the focus of light is strongly dis-
from BaTiO3 nanowires excited with a deep UV beam was used torted. To obtain a sharp image of the object, the SHG from a
to illustrate how the photo-excitation of BaTiO3 leads to modu- single BaTiO3 nanoparticle placed on the object was scattered
lations of χ(2) as a result of the local symmetry changes in the by the turbid medium and collected using a digital holographic
BaTiO3 crystal.[188] The coherence nature of the SHG signal microscope. Then, the distorted phase front was recreated by a
from BaTiO3 nanoparticles was also used for harmonic holo- spatial light modulator and sent back to the object behind the
graphic (H2) microscopy (Figure  10c). Using the SHG from turbid medium, where it arrived as focused light and was used
90 nm BaTiO3 nanoparticles inserted in a cell, it was possible to to obtain an image.[190]
obtain 3D imaging data without scanning.[189] In ultrafast nanoscale experiments, pulse shaping and com-
The coherent SHG signal from the BaTiO3 nanoparticles was pression are crucial for experiments on nanoscale structures
used to image an object located very close to a turbid or opaque from quantum dots to molecules. The SHG signal is used to

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www.advancedsciencenews.com
optimize such femtosecond laser pulses with the multiphoton
intrapulse interference phase scan (MIIPS) technique. For
such experiments, single BaTiO3 nanoparticles are a useful
source of coherent signal because they are a truly nanometric
volume. The SHG from a single BaTiO3 nanoparticle was com-
bined with a pulse shaper to obtain successful compression
of femtosecond laser pulses and control of the spectral phase
(Figure 10e).[191]
The nonlinear signal from a material can be strongly
enhanced in the vicinity of a plasmonic resonance. This
­principle is used in hybrid nanostructures containing BaTiO3
nanoparticles and a noble metal. One example is core–shell
nanoparticles, where a gold shell is chemically grown on a
BaTiO3 core. The gold shell acts as a plasmonic cavity that can
absorb and scatter light efficiently at chosen wavelengths. By
carefully tuning the ratio between the shell thickness and the
core radius, the plasmonic resonance of the cavity containing a
100 nm BaTiO3 nanoparticle was overlapped with the excitation
signal (Figure  11a). This resulted in a 500-fold enhancement
of the measured SHG from the core–shell nanoparticle.[192]
Core shell gold–BaTiO3 nanoparticles encapsulated in a silicon
oxide layer (Figure  11b) were used for plasmon enhanced dif-
ference frequency generation (DFG).[193] DFG is a second order
nonlinear process involving the annihilation of two photons
with different energy (pump and signal) and the emission of
a single photon with the difference of the original photons
Figure 11.  Single and complex BaTiO3 nanoparticle assemblies. a) Core–
shell nanoparticle of a BaTiO3 sphere with a chemically synthesized gold
coating. The gold shell acts as a plasmonic cavity and enhances the SHG
from the BaTiO3 by more than two orders of magnitude. Reproduced
with permission.[192] Copyright 2010, The Optical Society. b) Core–shell
Au–BaTiO3 nanoparticle encapsulated in SiO2. The core size and shell
thicknesses are tuned to have resonances for the wavelengths of the
pump, signal, and idler in the DFG process. Reproduced with permis-
sion.[193] Copyright 2016, American Chemical Society. c) BaTiO3 nanopar-
ticles covered with gold seeds, used for hyper Raman scattering to obtain
additional vibrational information about molecules. Reproduced with per-
mission under the terms of a CC-BY-NC-ND license.[194] Copyright 2019,
The Authors, published by Wiley-VCH. d) Capillarity-assisted particle
assembly in PDMS cavities is used to assemble hybrid BaTiO3–Au dimers.
Reproduced with permission.[129] Copyright 2017, American Chemical
Society. e) Hybrid BaTiO3–Au dimers are assembled by nanopositioning
with an AFM tip as shown in the SEM image. The SHG intensity and polar
response of these dimers can be tuned by modifying the sizes of the con-
stituting nanoparticles. Reproduced with permission.[130] Copyright 2019,
American Chemical Society.
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www.advopticalmat.de
energies (idler). The BaTiO3 core radius and the thicknesses of
the gold and SiO2 shells were designed such that the core–shell
nanoparticle has local field enhancement and far-field radiation
enhancement both for pump, signal and idler frequencies, such
that 7 × 10−7 idler photons were created per pump/signal photon
pair. The core shell nanostructure has potential as SPASER or
surface plasmonic enhanced optical parametric amplification.
Furthermore, BaTiO3 nanoparticles covered with gold or silver
nanoparticle seeds (Figure  11c) have a significant potential
as nanoprobes for combined multiphoton probing. These
hybrid nanoparticles have on one hand the harmonic signal,
and on the other hand offer an enhancement of the Raman
signal. This hyper Raman scattering technique offers a com-
plimentary vibrational information from molecules and can be
also used to probe environments.[194] BaTiO3 nanoparticles in
combination with metallic seeds also show an enhanced third
order nonlinearity, which makes them promising as contrast
agents, biosensors or phase conjugate nanomirrors.[119]
Another example of hybrid nanostructures are dimers con-
sisting of a BaTiO3 nanoparticle and a gold nanoparticle. Such
dimers have been successfully assembled by capillarity-assisted
particle assembly (Figure 11d)[129] or by nanopositioning with an
AFM tip (Figure 11e).[130] These techniques enable the combina-
tion of BaTiO3 and gold nanoparticles with different sizes and,
thus, the optical resonances can be tuned to the desired wave-
lengths or be overlapped to obtain hybrid resonances. The gold
nanoparticle also reshapes the polar response of the BaTiO3
nanoparticle, such that the SHG is maximized along the axis of
the hybrid dimer.
Finally, BaTiO3 nanoparticles in glycol solutions have
been used for high harmonic generation (HHG). This tech-
nique requires the creation of a BaTiO3 nanoparticle plasma
and results in coherent XUV radiation with attosecond time
scale.[113]
4.2. Photonic Metasurfaces
Photonic metasurfaces are utilized to engineer the spatio-
temporal properties of light at the subwavelength scale.[195]
Nanostructured thin films that form subwavelength optical
resonators (meta-atoms) support localized plasmonic[196]
(noble metal media) or Mie (dielectric media) modes,[197] there-
fore metasurfaces engineer the dispersion of light travelling
through or been reflected from them. Furthermore, arrays of
these meta-atoms, because of the subwavelength periodicity,
can obtain effective optical parameters at specific wavelengths
tuned by design. Photonic metasurfaces’ thickness usually
ranges from tens up to hundreds of nanometers and light is
coupled to them via out-of-plane light illumination. When the
meta-atoms are on resonance, the light–matter interaction
proliferates, thereby offer a platform for nonlinear enhance-
ment,[198] dispersion engineering,[199] optical sensing[200]
and active tuning of optical properties.[201,202] As a result, the
research agenda has been focused on the quest of either novel
designs to engineer strong light–matter interaction or novel
material platforms that can be used to improve the already
existing optoelectronic properties related to light emission,
higher harmonic generation and light modulation. BaTiO3 has
© 2020 The Authors. Published by Wiley-VCH GmbH
www.advancedsciencenews.com
Figure 12.  All-dielectric nonlinear array of BaTiO3/Si3N4 nanodisks.
a) Top-view SEM image corresponds to a section of the metasurface, inset
schematic of the sample geometry. b) Experimental setup for measuring
SHG. c) Polar plots of SHG signal emitted from metasurfaces of different
period (as annotated) and under different excitation wavelengths: 400 nm
(solid line), 450 nm (dashed line), and 500 nm (dotted line). Reproduced
with permission.[54] Copyright 2019, Wiley-VCH.
a relative high refractive index, thereby is a material platform
capable to support Mie type of optical resonances. While the
nonlinear and EO properties are adequate to assist on the for-
mation of active photonic metasurfaces.
Timpu et al.[54] developed the first all-dielectric BaTiO3 based
metasurface, which supported SHG signal, from near-ultravi-
olet up to the visible range. A bilayer film of BaTiO3 and Si3N4
nanostructured to an array of nanodisks via e-beam lithography.
The SEM image and the schematic of the nanodisk array are
presented in Figure  12 together with the experimental setup
and the SHG signal generated from the metasurfaces of sev-
eral periods as annotated. The SHG signal is improved in com-
parison to unstructured films, while the metasurface shapes
the polar distribution of the SHG signal. This is related to the
excitation of Mie modes from the periodic array of the BaTiO3/
Si4N3 nanodisks.
Other types of photonic metasurfaces were realized upon
the incorporation of plasmonic nanostructures and BaTiO3
nanocrystals. In Figure  13 are presented two such cases.
In the first case, Figure  13a–d is presented an electrooptic
metasurface.[203] It is formed by a subwavelength plasmonic
nanograting covered by a thin film of BaTiO3 nanoparticles.
Adv. Optical Mater. 2020, 8, 2001249 2001249  (18 of 23)
www.advopticalmat.de
The period of the metasurface was 550 nm, while the thickness
of the samples are 300 nm. The BaTiO3 nanoparticles have an
average diameter of 50 nm. Monochromatic light (at 1064 nm)
reflected by the metasurface, was dynamically modulated upon
application of sub-microsecond electric pulses. The nanopar-
ticle film had an effective EO coefficient of ≈37 pm V−1; larger
than several noncentrosymmetric EO crystals, see Table 1. The
advantage of this method is the use of BaTiO3 in the form of
nanoparticle solution, thereby employ a low cost method for the
production of ultrathin EO modulators. Further investigation of
domain formation in such complex films may be realized via
SHG measurements.[204] Similar EO response was also found
in a chemical solution deposited under atmospheric condi-
tions and yield an effective EO coefficient of 27 ± 4 pm V−1 for a
≈85 nm film of BaTiO3.[205]
By a novel two-step templated growth, a highly ordered
Au–BaTiO3–ZnO nanocomposite of self-assembled ZnO
nanopillars and Au nanopillars in a BaTiO3 matrix, was real-
ized.[206] They introduced a design of an epitaxial ordered
trilayer film (Au–BaTiO3–ZnO), by employing the vapor–
liquid–solid (VLS) mechanism, in combination with pulsed
laser deposition, the three-phase ordering was realized via
a combined self-assembly and templating method. BaTiO3
and ZnO allow the possibility of growing vertically aligned
nanocomposite BaTiO3–ZnO structure because of their phase
immiscibility and chemical compatibility. Driven by the ordered
growth of ZnO NWs via the VLS growth mechanism, the verti-
cally aligned Au nanopillars embedded in the template layer of
Au–BaTiO3 act as the seeds for catalyzing ZnO NW growth and
allow the highly ordered spatial control of ZnO nanostructures.
The Au–BaTiO3–ZnO metamaterials offer a material platform
of high tunability in their optical and electrical properties, such
as the hyperbolic dispersion in the visible and near infrared
regime, as illustrated in Figure 13e,f.
4.3. Photonic Crystals
Structures with periodic, spatial modulation of the refractive
index are called PhCs. 1D PhCs are structures with refractive
index modulation over a single direction. 2D PhCs corresponds
to planar arrays in periodic arrangement over a single plane,
while 3D PhCs have a 3D periodic ordering. PhCs platform
controls the light dispersion by engineering the energy band
structure for photons, which either allows or forbids the propa-
gation of electromagnetic waves of certain frequency ranges
and directions. In contrast to photonic metasurfaces PhCs have
periodicity comparable or larger than the incident wavelength,
while support long-range electromagnetic modes.
Liu et  al. reported integrated BaTiO3 PhCs.[207] They were
cascaded Bragg reflectors using a strip waveguide and made
by nanolithography for operation in near-infrared light. The
devices had a 27 nm wide stop band and were millimeter-long.
Other architectures that operate as 1D PhCs are based on multi-
layer structures, where sequence of alternating films of sol–gel
BaTiO3 films and either glassy or polymeric films.[171,208,209] The
applications were focused in terahertz generation or enhanced
photoluminescence. This configuration offers a simple yet pow-
erful tool to design photonic devices with low-cost and unique
© 2020 The Authors. Published by Wiley-VCH GmbH
www.advancedsciencenews.com www.advopticalmat.de

Figure 13.  Plasmonic metasurfaces based on BaTiO3. a–d) Electrooptic metasurface based on Au–BaTiO3 nanoparticle-films. a) Top-view and cross-­
section of EO metasurface. b) Optical field distribution for the resonant wavelength of 1064  nm. c) Electrooptic measurement setup, d) dynamic
reflection modulation up to 20 MHz. Reproduced with permission under the terms of a CC-BY-NC license.[203] Copyright 2020, The Authors, published
by Wiley-VCH. e) Au–BaTiO3–ZnO nanocomposites with absorption plasmonic resonances at 589 and 597 nm. Inset: cross-section TEM image of the
sample, with the different materials place annotated. f) Hyperbolic dispersion of the Au–BaTiO3–ZnO nanocomposite films. Reproduced with permis-
sion.[206] Copyright 2019, Wiley-VCH.

functionalities by combining different materials and film 5. Conclusions and Perspectives

thicknesses.[210]
BaTiO3 PhCs have also been realized in 2D arrangements.
Zhou et  al. fabricated SiO2 colloid opals infilled with BaTiO3
ferroelectrics and reported the temperature tuning of PBG in
this system.[211] Kim et  al. fabricated the similar compound
system by infilling BaTiO3 in SiO2 colloid opals,[212] Soten et al.
fabricated BaTiO3 inverse opals using polystyrene opals as
template,[213] while Hirano et al. fabricated 2D hexagonal arrays
of BaTiO3 pillars as PhCs.[214]
3D types of PhCs based on woodpile structures are reported
independently from Zhu et  al.[172] and Vogler-Neuling et  al.[58]
In the former case, the PhC lattice was directly written using
a 3D-printer to construct the woodpiles for application at
terahertz frequencies. They used a BaTiO3 ink embedded
in PDMS, with nozzle diameter of 180  µm to realize a PhC
with periodicity of 400 µm.  In the latter case, they employed
solution-­processed BaTiO3 nanoparticles in a polymeric matrix
to realize 3D photonic crystals. The woodpiles have the ben-
efit in comparison to other designs that can be made layer by
layer, thereby are a suitable platform for roll-to-roll fabrication
schemes, which can be easily adapted in industry. In this work,
woodpiles were made by UV-soft nanoimprint lithography,
comprise eight layers, with period of 1 µm and overall dimen-
sions of 1 cm2.
Photonic technologies demand highly integrated material plat-
forms with small power consumption and energy efficiency far
exceeding that of bulk optical components and silicon photonics.
We anticipate that robust and reliable operation of BaTiO3-based
devices may substitute silicon based photonic chips in optical
interconnects, as they possess excellent electric field tuning
capabilities. Furthermore, this multifunctional metal-oxide
material can promote integrated photonics in the race with elec-
tronics technology, not only in telecommunication networks, but
as well as applications such as smart phones and displays. We
expect that bottom-up fabrication methods will play an impor-
tant role to establish a low-cost/high yield production of nano-
films with highly responsive photonic and electronic properties.
Apart from traditional telecommunication systems, the
χ(2) nonlinearities of BaTiO3 and the electrooptic effect may
produce considerable breakthroughs in quantum optics and
microwave or THz to visible/near infrared transduction due to
the broad transparency range.
Last, the highly responsive nature of BaTiO3 (similar to
other ferroelectrics) associated with piezo-electric, pyro-electric
and thermo-electric properties may be the solution to provide
multifunctional nanodevices in the fields of sensing, energy
harvesting and heat control.

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www.advancedsciencenews.com
Acknowledgements
This work was supported by the Swiss National Science Foundation
Grant 179099, the European Union’s Horizon 2020 research and
innovation program from the European Research Council under the
Grant Agreement No. 714837 (Chi2-nano-oxides), the European Union’s
research and innovation Programme under the Marie Skłodowska-Curie
Grant agreement No 801459, FP-RESOMUS, the Swiss National Science
Foundation through the NCCR MUST, and the Marie Skłodowska-Curie
Grant agreement No. 800487 (SECOONDO). This article is part of the
Advanced Optical Materials Hall of Fame article series, which recognizes
the excellent contributions of leading researchers to the field of optical
materials science.
Conflict of Interest
The authors declare no conflict of interest.
Keywords
biophotonics, electrooptics, ferroelectrics, nanophotonics,
nanostructures, nonlinear optics
Received: July 23, 2020
Revised: September 14, 2020
Published online: November 5, 2020
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Artemios Karvounis received first his Ph.D. degree in 2018 and then continued as a research fellow
at the Optoelectronics Research Centre of the University of Southampton (United Kingdom).
In 2019, he joined the Optical Nanomaterial Group at the Physics Department of ETH Zurich
(Switzerland). In 2020, he became FP-RESOMUS fellow in the Swiss research network NCCR
MUST. The topics of his research include experimental nanophotonics, photonic metamaterials,
and the development of advanced optical materials.

Rachel Grange is an assistant tenure-track professor in the field of nonlinear integrated and
nanophotonics in the Department of Physics at ETH Zurich (Switzerland). From 2011 to 2014, she
was a group leader at the Friedrich Schiller University in Jena (Germany). Her research covers
material investigations at the nanoscale with high resolution imaging tools. She develops top-
down and bottom-up fabricated nanostructures with metal-oxides, mainly lithium niobate and
barium titanate. Her goal is to understand and control their behaviors to design versatile compact
photonic devices.

Adv. Optical Mater. 2020, 8, 2001249 2001249  (23 of 23) © 2020 The Authors. Published by Wiley-VCH GmbH