The fitting parameters in single layer model and graded layer model of the polycrystalline BFO films. Gaussian oscillator defined as following equation.
1. Introduction
1.1. Background
Lightwave communication systems are predominantly used for handling high-speed data traffic. Long-distance ground-based systems particularly depend on optical fibers. Several business and research facilities employ direct fiber connections, and fiber to the home (FTTH) technology is foreseeable in the near future. These developments are driven particulary by the high demand for bandwidth necessary for many computers contributing to internet traffic. Lightwave communication systems are one of the fastest growing industrial fields because of a few important inventions and extensive research and development by physicists and engineers. The key components of a long-distance lightwave communication system are semiconductor lasers, low-loss glass fibers, optical amplifiers, and photodetectors. Apart from these key elements, several additional functions are required to enable modulating, switching, and combining the optical signals. In addition, network traffic management and switching, routing, and distribution systems are essential. Therefore, we focused on the development of optical components such as modulators and switches.
Here, some of the novel optical devices for modulating or switching light signals are introduced. First, the operating principle of an electro-optic spatial light modulator (EOSLM) is described. In general, a spatial light modulator is an optical device that achieves spatial modulation of incident light. Figure 1(a) shows the basic structure of an optical switching cell in an EOSLM. [1, 2] An electro-optic thin film is fabricated on a large-scale integration (LSI) circuit together with top and bottom electrodes. The top electrode is made of transparent conductive material such as indium tin oxide (ITO). A dielectric multi-layer mirror (DMM) is deposited onto the ITO electrode, and a Fabry-Perot resonator is formed between the upper mirror and the bottom platinum electrode. In this case, the minimum reflectance becomes zero because the reflectance of the DMM and the bottom Pt layer is the same. If the refractive index can be controlled by applying an electric field, the cell can switch incident light at a specific wavelength as shown in Fig. 1(b).
Next, the operating principle of a Mach-Zehnder modulator (MZM) is described. Figure 2 shows a schematic diagram of an electrooptic-type MZM. [3-5] Incident light is split into two waveguides. The output amplitude depends on the phase difference at recombination. As shown in the top right part of the figure, in-phase recombination produced a “1” bit output while anti-phase recombination produces a “0” bit output owing to half-wave phase shifting caused by an applyied voltage. A half-wave phase shift can be caused by either the electro-optic effect or the thermo-optic effect. When using the thermo-optic effect, the optical switch structure includes a heater on one side of the waveguide instead of a top electrode. [6,7]
To realize these novel thin-film optical devices, many researchers have intensively studied materials that exhibit the electro-optic effect. Traditional electro-optic materials include (Pb,La)(Zr,Ti)O3 (PLZT) and LiNbO3. PLZT is the most promising candidate for such applications because it has a high transparency in its polycrystalline form. [7] It is well known that bulk PLZT with a 65:35 Zr:Ti ratio shows large electro-optic effect coefficients: a Pockels coefficient (linear electro-optic coefficient) of 6.12 × 10 -10 m/V and a Kerr coefficient (quadratic electro-optic coefficient) of 9.12 × 10 -16 m2/V2 with La contents of 8 and 9 at.%, respectively. [8] The next generation of new multiferroic materials, such as BiFeO3 (BFO), which exhibits a giant remanent polarization of 100 μC/cm2 in the thin-film form, [9,10] is now reaching maturity and has recently attracted considerable attention because of its potential applications in novel multifunctional devices. In recent years, the electric and magnetic properties of BFO films have been a topic of intense research, with regard to their magnetoelectric (ME) effect [11-13], while few reports on their optical properties have been published. [14-16] Therefore, it is necessary to know the basic optical properties of BFO films, such as the optical constant and thermooptic property, for the development of various optical applications. Understanding the optical potential in multiferroic materials leads us to additional noble material selections and thus degrees of freedom.
1.2. Objectives
To realize smaller and faster optical modulators or switches, it is necessary to embed electro-optic or thermo-optic materials in semiconductor integrated circuits. Accordingly, we have investigated the electro-optic and thermo-optic coefficients of materials in polycrystalline film form. We explain in detail the optical property evaluation method used in this study to exclude extrinsic effects, and then, we carefully determine the basic optical and thermo-optical properties of multiferroic BiFeO3 polycrystalline films. Finally, we would like to understand the potential application of these optical properties to noble multifunctional devices using multiferroic BiFeO3 polycrystalline films. This chapter describes the basic film preparation method and the basic method for evaluation of optical properties to increase understandings for beginner in this research field.
1.3. Outline of this chapter
This chapter is divided into 4 sections. Section 1 describes the background and objective of this study. In Section 2, we summarize the fundamentals of multiferroic BiFeO3 used in this study, the method for fabricating multiferroic thin films, the basic optics principles related to this study, and the detailed method for evaluating optical properties. In Section 3, we discuss the thermooptic effect of multiferroic BFO films. The polycrystalline BFO films are fabricated on Pt/Ti/SiO2/Si substrates, respectively. First, their fundamental properties are evaluated. Next, the optical constants of these films are evaluated as a basic optical property. In Section 4, we summarize the conclusions of this chapter.
2. Experimental procedures
2.1. Fundamentals
Ferroelectricity is a property of certain materials that allows for spontaneous reversible electric polarization by applying an external electric field. The ability of a crystal to exhibit spontaneous polarization is related to its symmetry. Of the 32 point groups, which describe all crystalline systems, 11 are centrosymmetric and contain an inversion center. The remaining 21 point groups without an inversion center can exhibit piezoelectricity, except for the point group
In this chapter, the fundamentals of materials, fabrication, and evaluation are mentioned. In particular, the basic characteristics of BiFeO3 potential ferroelectric films are mentioned together with their optical properties.
2.2. BiFeO3 multiferroics
Perovskite-oxide has a structural formula of ABO3, in which A is a large cation such as Bi3+, Ba2+, or Pb2+, and B is a medium-sized cation such as Fe3+, Ti4+, or Zr4+. These cations are located in cages formed by a network of oxygen anions, as shown in Fig. 3(a). Ferroelectric perovskites are a subgroup of the perovskite family. They are cubic at high temperatures and become polar non-cubic,
Multiferroic materials have more than one primary ferroic order parameter such as ferroelectricity, ferromagnetism, and ferroelasticity in the same phase. Multiferroic materials have attracted considerable attention, not only in terms of scientific interest but also because of their potential applications in novel functional devices. Bismuth ferrite (BiFeO3, BFO) has long been known to be a multiferroic material that exhibits antiferromagnetism (
The Fe magnetic moments are coupled ferromagnetically within the pseudocubic (111) planes and antiferromagnetically between the near planes; this is called the
According to a first-principles calculation, the spontaneous polarization of BFO changes depending on whether the crystal structure is rhombohedral or tetragonal. The tetragonal structure of the BFO (SG:
2.3. Fabrication method
2.3.1. Preparation method using chemical solution deposition
Chemical solution deposition (CSD) [26] is the method for fabrication of thin films using a precursor solution; several types of metal-organic compounds such as metal alkoxide and metal carboxylate compounds can be used as the precursor solution. The fabrication of thin films by this approach involves four basic steps:
Synthesis of the precursor solution;
Deposition by spin-casting or dip-coating, where the drying processes usually depends on the solvent;
Low-temperature heat treatment for drying, pyrolysis of organic species (typically 300–400°C), and formation of an amorphous film;
Higher-temperature heat treatment for densification and crystallization of the coating into the desired oxide phase (600–1100°C).
For most solution deposition approaches, the final three steps are similar despite differences in the characteristics of the precursor solution, and for electronic devices, spin-casting has been used almost exclusively. Depending on the solution route employed, different deposition and thermal processing conditions may be used for controlling film densification and crystallization in order to prepare materials with optimized properties.
For the fabrication of perovskite thin films, the most frequently used CSD approaches may be grouped into three categories:
Sol-gel processes that use 2-methoxyethanol as a reactant and solvent.
Chelate processes that use modifying ligands such as acetic acid.
Metal-organic decomposition (MOD) routes that use water-insensitive metal carboxylate compounds.
Other approaches that have also been used, although less extensively, include the nitrate method, citrate route, and Pechini process. In this study, a sol-gel solution and an enhanced-MOD (EMOD) solution (symmetric) were used because of their manageability.
2.3.2. Synthesis of the precursor solution for CSD
Processes based on 2-methoxyethanol are most appropriately considered sol-gel processes, and the key reactions leading to the formation of the precursor solutions are hydrolysis and condensation of the alkoxide reagents, in which metal-oxygen-metal (M-O-M) bonds are formed:
Hydrolysis:
Condensation:
In some cases, an alcohol exchange reaction occurs in a practical synthesis process.
Alcohol exchange:
where OR is a reactive alkoxy group and OR’ is the less reactive methoxyethoxy group.
In addition, to prepare a compound oxide material using two or more kinds of metal compounds in order to increase the homogeneity of the precursor solution, a double alkoxide with M-O-M’-O bonds may be synthesized for refluxing in an inactive gas atmosphere.
Synthesis of double alkoxide:
In addition, if a metal alkoxide and carboxylate compounds are used, the synthesis is occasionally accompanied by an esterification reaction.
Esterification reaction:
For reproducible thin films, byproducts such as esters produced during the synthesis should be removed from the precursor solution through fraction distillation.
2.3.3. Preparation conditions of BFO polycrystalline films
The BFO films were formed through CSD. A precursor solution for CSD was prepared from bismuth acetate (99.99%, Aldrich), iron acetylacetonate (99.9%, Wako) in a solvent of 2-methoxyethanol (99.7%, Aldrich), and acetic acid (99.5%, Wako). The solution was heated to 80–100oC while stirring for 30 min to promote the dissolution of the precursors, followed by stirring at RT for 1 day before film deposition. The solution was synthesized on the basis of a stoichiometric composition. The concentration of the precursor solution was adjusted to be 0.05 M.
Figure 5 shows the process flow for the fabrication of the polycrystalline BFO film through CSD. A (111)Pt/Ti/SiO2/(100)Si substrate was spin coated with the precursor solution at 3000 rpm for 30 s. The spin-coated film was dried at 150oC for 1 min and pyrolized at 400oC for 2 min in air. After the processes from spin coating to pyrolysis were repeated 10 times, the film was fired at 550oC for 5 min in air through rapid thermal annealing (RTA). This sequence was repeated 10 times. The film was polycrystalline with a random orientation and was approximately 650 nm thick.
2.4. Optical properties of ferroelectrics
2.4.1. Refractive index
The general definition of refractive index
where
This relationship is only valid when the interacting electric field has a frequency on the order of THz or higher and when the material is isotropic. The general behavior of condensed matter in an alternating electric field is that moving charges cause a frequency-dependent phase shift between the applied field and the electric displacement. Mathematically, this is expressed by writing the permittivity
The real part
Since light is an alternating electromagnetic wave with the electric and magnetic field vibration directions perpendicular to one another, the electric field induces an electric polarization in a dielectric crystal and the light itself is influenced by the crystal. The alternating frequency of light is so high (λ= 500 nm corresponds to a frequency of approximately 600 THz) that only electronic polarization can follow the electric field change. Therefore, the relative permittivity of an optically transparent crystal is small, typically less than 10. It is known that a dielectric material shows wavelength dispersion of its refractive index at optical frequencies.
2.4.2. Optical indicatrix and anisotropy of refractive index
In a microscopically anisotropic medium, the refractive index is generally different for different crystal directions. Ferroelectric materials, particularly in film form, can be both optically isotropic and optically anisotropic. Ferroelectric ceramics or polycrystalline films are an example of the former type; their isotropic behavior is due to the random orientation of their constituent grains. Ferroelectric single crystals or epitaxial films are an example of the latter type, and they can be divided into optically uniaxial and optically biaxial crystals. If a coordinate system is chosen to coincide with the three principal axes of a crystal, we have the following relations:
The optical anisotropy of a crystal is characterized by an optical indicatrix (or index ellipsoid) defined as
where
In the case of a biaxial crystal, there are two optical axes, and the refractive indexes are different in all three principal directions,
Since the value of
2.4.3. Thermooptic effect
The thermo-optic effect refers to thermal modulation of the refractive index of a material. The refractive index of a material can be modulated as a function of its thermooptic coefficient
where
2.5. Evaluation method of optical properties
Ellipsometry determines the optical constants and thickness of materials in layered samples by fitting a parameterized model to the measured data for simultaneously analyzing data from multiple samples. Figure 7 shows a schematic illustration of ellipsometry. The linearly polarized incident light is reflected after interacting with the sample. The polarization of the light changes from linear to ellipsoidal from this interaction. We measure the polarization state using the ratio of the reflection coefficients for the light polarized parallel (
where
For
and for
Here, ñ is the complex refractive index, and
In this study, a Gaussian oscillator was used to model a dielectric function to represent film properties. Gaussian oscillators represent the normal distribution for the
where
where
3. Optical properties of multiferroic BiFeO3 films
3.1. Fundamentals
Multiferroic materials, which simultaneously exhibit ferroelectricity and magnetic ordering, have attracted considerable attention, not only in terms of scientific interest but also because of their potential applications in novel functional devices. BFO is one of the few materials that exhibit dielectric and magnetic ordering at room temperature. [17,18] BFO also exhibits a large remanent polarization of 100 μC/cm2 in thin film form. [9,10] Therefore, the electric and magnetic properties of BFO films have been the subject of intense research in recent years. [11-13] However, few reports on their optical properties [14,15] or their applications [16] have been published. It is important to know the exact optical properties of BFO films in order to develop various optical applications. To apply BFO films to optical devices, the electro-optic, magneto-optic, and thermo-optic effects of the films can be controlled by modulating their refractive indices. Recently, a Mach-Zehnder-type optical switch, which employs the thermo-optic effect, is a topic of immense interest in the photonics field. [33-35] In this section, we examine the optical constant and the temperature dependence of the refractive index of polycrystalline BFO films.
3.2. Experimental machines
Crystal structure and orientation: X-ray diffractometer (PANalytical, X’pert PRO MPD)
Morphology: field emission scanning electron microscope (JEOL, JIB-4500FE), transmission electron microscope (Hitachi, HF-2000), atomic force microscope (SII, SPI3800N)
Electrical property: ferroelectric test system (Toyo, FCE)
Optical property: spectroscopic ellipsometer (J. A. Woollam, M-2000) with a heating stage, as shown in Fig. 8( a) and 8(b).
3.3. Fundamental properties of polycrystalline BFO film
Polycrystalline BFO films were successfully formed on the Pt/Ti/SiO2/Si substrates through CSD. Figure 9 shows the XRD
Figure 10 shows the
Figure 11 shows a) the surface morphology and the cross-sectional images of (b) the cleavage face and (c) the worked surface using a focused ion beam. From Fig. 11(a) and (b), it can be seen that the polycrystalline BFO film consists of small randomly grown grains, whereas the bottom Pt layer has a columnar grain growth. From Fig. 11(c), voids in the film were confirmed. Film thickness was estimated to be approximately 650 nm from cross-sectional images.
3.4. Optical constants of polycrystalline BFO film
Ellipsometric spectra in (∆, ψ) were recorded at tincident angles of θi = 50o, 60o, and 70o in a spectral range of 245–1670 nm. Figure 12 shows the multilayer model used in this study. It was assumed that the model consisted of ambient (air), a surface layer, a bulk layer, and a substrate (Pt). The optical constants of the surface layer were represented by the Bruggeman effective medium approximation (EMA) [37] consisting of a 0.50 bulk film/0.50 void mixture. In the polycrystalline BFO film, 4 Gaussian oscillators were assumed to represent the film properties. Furthermore, the density gradient along the film thickness, which affects the refractive index gradient, was also introduced by applying the EMA. Figure 13(a)–(d) shows the
Figure 14 shows the optical constant of the polycrystalline BFO film in the wavelength range of 245 - 1670 nm calculated from the best-fitting results. In Fig. 14, the solid and broken lines represent the maximum and minimum values, respectively, of each optical constant in the graded layer. A large refractive index of 3.22 was estimated for the polycrystalline BFO film; this value is higher than that of rutile-type TiO2 film, which has the highest refractive index among oxides reported thus far. At a wavelength of 600 nm, the refractive index of our BFO film was 3.22 and that of the TiO2 film was reported to be approximately 2.6. [38] Figure 15 shows the depth profile of the refractive index and the extinction coefficient of the BFO film at a wavelength of 500 nm. This profile shows that the refractive index near the substrate is larger than that at the surface area. The reason for this gradient is not yet clear, although one possible explanation is the existence of voids in the film.
To determine the optical band gap, we plot (
where
3.5. Thermooptic property of polycrystalline BFO film
3.5.1. Temperature dependence of lattice space
Figure 17 shows the lattice spacing of Si (400), BFO (100), and Pt (111) as a function of temperature, estimated from XRD patterns. All the
3.5.2. Temperature dependence of refractive index
Ellipsometric spectra in (Δ,
Figure 19 shows the temperature dependence of the refractive index in a long- wavelength region. It is found that refractive index decreases with increasing temperature at each wavelength, although there was some variability. The thermo-optic coefficient was estimated from the slopes of linear approximation. A thermo-optic coefficient of 0.8 × 10 -4 K-1 was obtained at a wavelength of 1550 nm for the BFO film. The thermo-optic coefficients of polymers and glasses, which are known to be typical thermo-optic materials, have been reported to be approximately 2 × 10 -4 K-1 and 0.1 × 10 -4 K-1, respectively. [45,46] It is found that the BFO film shows a large refractive index and a thermo-optic coefficient comparable to that of these traditional materials. Finally, it can be concluded that the BFO also has potential for use in an electro-optic-type Mach-Zehnder modulator.
4. Conclusions
The optical and thermo-optic properties of BiFeO3 (BFO) films were studied. Polycrystalline BFO films were formed on Pt/Ti/SiO2/Si substrates, and their basic optical and thermo-optic properties were systematically evaluated. The new findings are summarized as follows:
The polycrystalline BFO films were evaluated using a spectroscopic ellipsometer. Gaussian oscillators were assumed as a dielectric function to represent film properties, and the graded model was assumed by introducing a refractive index gradient. As a result, large refractive indexes of 3.22 and 2.91 were estimated for the polycrystalline BFO film at wavelengths of 600 and 1550 nm, respectively, these refractive indexes are higher than that of the rutile-type TiO2 film, which is known to have a high refractive index. The optical band gap of the BFO film at RT was estimated as a direct transition to be 2.79 eV, which corresponds to the absorption edge of 445 nm. It was found that the BFO film shows sufficiently low light loss at wavelengths larger than 600 nm.
The thermo-optic properties of the BFO films were evaluated using a spectroscopic ellipsometer with a heating stage. The refractive index of the polycrystalline film decreased with increasing temperature. We considered that this change in refractive index is caused by the balance between the increase in refractive index due to the enhancement of the oscillator dispersion and the decrease in refractive index due to the decreased density of the film. In addition, we obtained thermo-optic coefficient of 0.8 × 10- 4 K-1 at a wavelength of 1550 nm for the BFO film, which is larger than those of typical thermo-optic polymers (2 × 10- 4 K-1) and glasses (0.1 × 10 -4 K-1).
These results suggested that the BFO films have a high potential for application as an optical material with a high refractive index, and that the effectual refractive index change can be controlled by the balance of two factors, the activation of the oscillator and the thermal expansion coefficient, even in the same material.
Acknowledgments
The author thanks Assistant Prof. Takashi Nakajima, Tokyo University of Science, Prof. Akiharu Morimoto, Asso. Prof. Takeshi Kawae, Kanazawa University, Prof. Takashi Yamamoto, Ass. Prof. Ken Nishida, National Defense Academy, Dr. Takashi Iijima, AIST, Dr. Koichi Tsutsumi, Dr. Masahiro Matsuda, Dr. Michio Suzuki, J. A. Woollam Japan, and Dr. Toshiyasu Tadokoro Techno-Synergy, Inc. This study was partially supported by a Grant-in-Aid for JSPS Research Fellows (No. 217990) from the Japan Society for the Promotion of Science.References
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