TY - JOUR
T1 - Stabilization of Size-Controlled BaTiO3Nanocubes via Precise Solvothermal Crystal Growth and Their Anomalous Surface Compositional Reconstruction
AU - Nakashima, Kouichi
AU - Onagi, Kaito
AU - Kobayashi, Yoshio
AU - Ishigaki, Toru
AU - Ishikawa, Yoshihisa
AU - Yoneda, Yasuhiro
AU - Yin, Shu
AU - Kakihana, Masato
AU - Sekino, Tohru
N1 - Funding Information:
This work was supported by JSPS KAKENHI Grant Numbers JP16K05931 and JP19K05644 and Asahi Glass Foundation. In addition this work was performed under the Research Program of the "Dynamic Alliance for Open Innovation Bridging Human, Environment and Materials" in the "Network Joint Research Center for Materials and Devices" grant number 20203028, and was supported by "The JAEA and QST Advanced Characterization Nanotechnology Platforms" of the Ministry of Education, Culture, Sports, Science and Technology (MEXT) Japan, grant number JPMXP09A20AE0023. The ND experiments at the Materials and Life Science Experimental Facility of the J-PARC were performed under a user program (grant numbers 2019PM2012 and 2020PM2008). This work was also supported by the Advanced Characterization Platform of the Nanotechnology Platform Japan sponsored by the MEXT, Japan grant numbers JPMXP09A19KU0297 and JPMXP09A20KU0341. We are grateful to Takaaki Toriyama and Masaki Kudo of Kyushu University for helpful support in the STEM analysis. Additionally, we are grateful to Hiroshi Kageyama of Kyoto University for his advice related to surface reconstruction to Junji Yamanaka for his assistance with TEM and STEM analyses at the University of Yamanashi, and to Shunsuke Kayamori for his helpful support with SE observations at Tohoku University.
Funding Information:
This work was supported by JSPS KAKENHI Grant Numbers JP16K05931 and JP19K05644 and Asahi Glass Foundation. In addition, this work was performed under the Research Program of the “Dynamic Alliance for Open Innovation Bridging Human, Environment and Materials” in the “Network Joint Research Center for Materials and Devices”, grant number 20203028, and was supported by “The JAEA and QST Advanced Characterization Nanotechnology Platforms” of the Ministry of Education, Culture, Sports, Science and Technology (MEXT), Japan, grant number JPMXP09A20AE0023. The ND experiments at the Materials and Life Science Experimental Facility of the J-PARC were performed under a user program (grant numbers 2019PM2012 and 2020PM2008). This work was also supported by the Advanced Characterization Platform of the Nanotechnology Platform Japan sponsored by the MEXT, Japan, grant numbers JPMXP09A19KU0297 and JPMXP09A20KU0341. We are grateful to Takaaki Toriyama and Masaki Kudo of Kyushu University for helpful support in the STEM analysis. Additionally, we are grateful to Hiroshi Kageyama of Kyoto University for his advice related to surface reconstruction, to Junji Yamanaka for his assistance with TEM and STEM analyses at the University of Yamanashi, and to Shunsuke Kayamori for his helpful support with SE observations at Tohoku University.
Publisher Copyright:
© 2021 The Authors. Published by American Chemical Society.
PY - 2021/4/13
Y1 - 2021/4/13
N2 - Crystal growth of barium titanate (BaTiO3) using a wet chemical reaction was investigated at various temperatures. BaTiO3 nanoparticles were obtained at an energy-efficient temperature of 80 °C. However, BaTiO3 nanocubes with a preferred size and shape could be synthesized using a solvothermal method at 200 °C via a reaction involving titanium tetraisopropoxide [(CH3)2CHO]4Ti for nucleation and fine titanium oxide (TiO2) nanoparticles for crystal growth. The BaTiO3 nanocubes showed a high degree of dispersion without the use of dispersants or surfactants. The morphology of BaTiO3 was found to depend on the reaction medium. The size of the BaTiO3 particles obtained using water as the reaction medium was the largest among the particles synthesized using various reaction media. In the case of alcohol reaction media, the BaTiO3 particle size increased in the order methanol, ethanol, 1-propanol, 1-butanol, and 1-pentanol. Furthermore, BaTiO3 powder obtained using alcohol reaction media resulted in cubic shapes as opposed to the round shapes obtained when water was used as the medium. We found that the optimal condition for the synthesis of BaTiO3 nanocubes involved the use of 1-butanol as the reaction medium, resulting in an average particle size of 52 nm, which is the average distance of the cubes measured diagonally from corner to corner, and gives an average side length of 37 nm, and a tetragonal crystal system as evidenced by the powder X-ray diffraction pattern obtained using high-energy synchrotron X-rays. The origin of the spontaneous polarization of the BaTiO3 tetragonal crystal structure was clarified by a pair distribution function analysis. In addition, surface reconstruction of BaTiO3 nanocubes led to an outermost surface comprising two layers of Ti columns.
AB - Crystal growth of barium titanate (BaTiO3) using a wet chemical reaction was investigated at various temperatures. BaTiO3 nanoparticles were obtained at an energy-efficient temperature of 80 °C. However, BaTiO3 nanocubes with a preferred size and shape could be synthesized using a solvothermal method at 200 °C via a reaction involving titanium tetraisopropoxide [(CH3)2CHO]4Ti for nucleation and fine titanium oxide (TiO2) nanoparticles for crystal growth. The BaTiO3 nanocubes showed a high degree of dispersion without the use of dispersants or surfactants. The morphology of BaTiO3 was found to depend on the reaction medium. The size of the BaTiO3 particles obtained using water as the reaction medium was the largest among the particles synthesized using various reaction media. In the case of alcohol reaction media, the BaTiO3 particle size increased in the order methanol, ethanol, 1-propanol, 1-butanol, and 1-pentanol. Furthermore, BaTiO3 powder obtained using alcohol reaction media resulted in cubic shapes as opposed to the round shapes obtained when water was used as the medium. We found that the optimal condition for the synthesis of BaTiO3 nanocubes involved the use of 1-butanol as the reaction medium, resulting in an average particle size of 52 nm, which is the average distance of the cubes measured diagonally from corner to corner, and gives an average side length of 37 nm, and a tetragonal crystal system as evidenced by the powder X-ray diffraction pattern obtained using high-energy synchrotron X-rays. The origin of the spontaneous polarization of the BaTiO3 tetragonal crystal structure was clarified by a pair distribution function analysis. In addition, surface reconstruction of BaTiO3 nanocubes led to an outermost surface comprising two layers of Ti columns.
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U2 - 10.1021/acsomega.0c05878
DO - 10.1021/acsomega.0c05878
M3 - Article
AN - SCOPUS:85104920321
VL - 6
SP - 9410
EP - 9425
JO - ACS Omega
JF - ACS Omega
SN - 2470-1343
IS - 14
ER -