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1/14/11

Barium titanate nanocrystals

Barium titanate

Barium titanate (BaTiO3) is a classical ferroelectric material belonging to the group of perovskite materials. The molecular formula is BaTiO3, relative molecular weigh is about 233. 24. BaTiO3 has upper dielectric constant and piezoelectricity performance and is an important ferroelectric material. Barium titanate (BaTiO3) is the most studied, have received tremendous research attention in the past decades due to their unique ferroelectric, catalytic, sensing, superconducting, and optical properties for use in thin-film capacitors, pyroelectric detectors, electro optic modulators, transducers, actuators, optical memories, and nonlinear optics.
Uses of barium titanate
Barium Titanate(BaTiO3) of high purity and low particle size of 0.1-0.5um, is widely applied to the field of specific electronic ceramics such as MLCC, PTC, microwave dielectric ceramic etc. Nanoceramics
Nanoceramic functional particles are difficult to handle and process because of the high surface area to volume ratio of these particles.
Uses of nanoceramics
Nanosize dielectric ceramic particles are used in the development of volume-efficient multilayer ceramic capacitors (MLCCs). Barium titanate (BaTiO3 : BT) is one of the most important dielectric material widely used for MLCCs and future nano-electronics. Ceramic-based nano composites have the potential to yield materials with enhanced permittivity, breakdown strength (BDS), and reduced strain, which can increase the energy density of capacitors and increase their shot life.
Barium titanate nanomaterials
Barium titanate nanoparticles, nanopowder, nanodots or nanocrystals are spherical or faceted high surface area nanocrystalline alloy particles with magnetic properties. Nanoscale barium titanate particles are typically 20-40 nanometers (nm) with specific surface area (SSA) in the 30 – 50 m 2 /g range and also available in with an average particle size of 100 nm range with a specific surface area of approximately 7 m 2 /g. Nano barium titanate particles are also available in ultra high purity and as coated and dispersed forms.
Synthesis of BT
Various approaches have been explored for the synthesis of BaTiO3 nanocrystals, such as injection-hydrolysis, thermal decomposition, and peptide assisted precipitation, none to date have enable shape control. To overcome this limitation, ISU researchers have developed a one-pot non-hydrolytic approach for shape controlled synthesis of ferroelectric BaTiO3 nanocrystals. By tuning the molar ratio between the surfactant and metal precursors, BaTiO3 nanocrystals with different shapes, such as nanoparticles, nanorods, and nanowires, can be obtained.
In an industrial scale, BT powders are synthesized by a solid state reaction at high temperatures using hydrothermal method which has a special advantage over conventional solid state reaction due to the quasi-atomic dispersion of Ba2+ and Ti4+ in a liquid precursor, leading to a nucleation and crystallization process occurring at low temperatures under a high pressure, yielding high purity particles.
BT nanocrystals are synthesized by controlling the nucleation and growth by modifying the surface inhibiting further growth. The growth inhibitor adsorbate may also be utilized as a built-in dispersant for processing of the powder. For the Synthesis of BaTiO3 nanocrystals, nanowires and nanotubes synthesis methods include hydrothermal/solvothermal synthesis, co precipitation and sol-gel processing, pyrolysis and decomposition of bimetallic alkoxide precursors in the presence of coordinating ligands, liquid-solid-solution phase transfer, peptide templates assisted room temperature synthesis, low temperature aqueous synthesis with seed-mediated growth method and sol-precipitation route.
Using BaCl2 and TiCl4
When nano BT is synthesized by using an aqueous solution of BaCl2 , it is mixed with an aqueous solution of TiCl4. Polyoxyethylene sorbitan monooleate is added as a polymeric stabilizer into above solution at a concentration of 5.0 wt%. A high pH is maintained by KOH. The resulting milky sol is filled in a high-pressure stainless steel vessel and heated to 100oC ~ 230oC for 10 min to 2 h. The resultant nanocrystals are washed with deionized water and dried to get nano BT.
Bimetallic BaTi molecular precursor: Barium titanium glycolate (BTG)
In another procedure for BaTiO3 nanocrystal synthesis, a single bimetallic molecular precursor was used to ensure a correct stoichiometry of the product. The BaTi precursor barium titanium glycolate BaTi C2H4O2 34C2H6O2H2O was first prepared in a dry box by mixing BaO, ethylene glycol, 2-propanol, and Ti OPr 4. The resulting white powder was filtered, washed, dried at 60 °C, and kept in dry box because of its hygroscopic property.
Hydrothermal technique
Nanocrystalline barium titanate was synthesized by the hydrothermal technique at low temperature and atmospheric pressure, an optimum synthesizing temperature in the hydrothermal technique is found at 80 °C, at which the as-prepared nanocrystal barium titanate shows an excellent lattice structure and the strongest PL at room temperature.
Barium titanate was synthesized using a wet chemical technique followed by a high temperature and high-pressure hot isostatic pressing treatment and can be a processing step toward the ability to prepare textured films based on assembly of nanoparticles. Essential to this approach is an understanding of the nanoparticle as a building block, combined with an ability to integrate them into thin films that have uniform and characteristic electrical properties. This method offers a versatile means of preparing BaTiO3 nanocrystals, which can be used as a basis for micro patterned or continuous BaTiO3 nanocrystal thin films. We observe the BaTiO3 nanocrystals crystallize with evidence of tetragonality. We investigated the preparation of well-isolated BaTiO3 nanocrystals smaller than 10 nm with control over aggregation and crystal densities on various substrates such as Si, Si/SiO2,Si3N4 / Si, and Pt-coated Si substrates. BaTiO3 nanocrystal thin films were then prepared, resulting in films with a uniform nanocrystalline grain texture.
Sol-gel method
The sol-gel method for obtaining nanocrystalline particles of BaTiO3 is relatively simple and easy to carry out. This method has a few important advantages in comparison to the conventional solid state method (SSM). The sol-gel route is less expensive (temperatures lower than 1000 deg.C), enables a high concentration of dopant to be introduced, and assures a better control of reaction conditions such as pH or temperature. The sol-gel type synthesis from a bimetallic alkoxide precursor in conjunction with a solvothermal technique produces crystalline particles with controllable size. The other method involves the organic-metallic reaction of the bimetallic alkoxide precursor with hydrogen peroxide at high temperature. This procedure forms monodisperse BaTiO3 particles that are soluble in non-polar solvents.
Solvothermal reaction of a mixture of metallic barium and titanium isopropoxide in acetophenone leads to the formation of barium titanate nanocrystals.
BaTiO3 nanocrystallites
For the preparation of BaTiO3 nanocrystallites barium acetate, titanium butoxide and neodymium oxide were used as starting materials. Acetylacetone and acetic acid were selected as solvents for titanium butoxide and barium acetate, respectively. Neodymium chloride was obtained by reacting stoichiometric amounts of neodymium oxide with hydrochloric acid. Dissolved barium acetate was added drop wise to titanium butoxide solution while stirring. The obtained solutions were vigorously stirred at 50 deg.C for about 2 h. The neodymium salt was dissolved in a small amount of water and added slowly to the obtained transparent yellow sol with specific molar ratios of Nd3+ to BaTiO3. The sol obtained was heated at approximately 100 deg. C for 24 h to form barium titanate gel. The crushed gel was heated above 700 deg.C to form nanocrystalline BaTiO3 powders doped with Nd3+. The average size ranged between 30 and 60 nm, depending on the dopant concentration and sintering temperature.
In another procedure thin laminates (thickness 20-45 nm) of barium titanate, BaTiO3 (BT), have been synthesized by the sol-gel method followed by heating of the amorphous precursor powder in air. An orthorhombic BT polymorph forms along with a tetragonal phase (t-BT) after 2 h of heating the precursor at 600°C, as evidenced by a well-defined X-ray diffraction pattern.
Uses of nanocrystals
These nanocrystals may have utility as nanoscale modules for the assembly of various electronic devices, such as sensors, detectors, capacitors, etc; in addition, BaTiO3 nanocrystals can also be used in multifunctional structural capacitors (where material elements simultaneously carry load and store energy) and related transducers and sensors.Barium titanate (BaTiO3) is a material that has potential as a data storage medium that can be read optically and written electrically, since it is both ferroelectric and birefringent.
There are several advantages of using these materials for data storage since they maintain their polarization state after the applied voltage has been removed, they do not require back up memories or batteries. They can be accessed more quickly and with less power than many memory devices, which need to push electrons through a glass barrier. Additionally, they have potential for increased miniaturization.

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