• Journal of the Korean Ceramic Society
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• v.35 no.11
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• pp.1130-1140
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• 1998

Thin films of $Bi_4Ti_3O_{12}\;nBaTiO_3(n=1&2)$ were prepared using sols erived Ba-Bi-Ti complex alkoxides. The sols were spin-cast onto $Pt/Ti/SiO_2/Si$ substrates and followed by pyrolysis for 1 hr at $620^{\circ}C,\;700^{\circ}C\;and\;750^{\circ}C$ In the thin films a pyrochlore phase seemed to be formed at a lower temperature and then tran-formed to the layered perovskite phase as the heating temperature increased. In the thin films pyrolyzed at formed to the layered perovskte phase as the heating temperature increased. In the films pyrolyzed at $750^{\circ}C$ the amount of $Bi_4Ti_3O_{12}{\cdot}BaTiO_3$ reached to 94% while $Bi_4Ti_3O_{12}{\cdot}BaTiO_3$ was 77% in composition. This result shows that the formation of the layered pervoskite phase becomes difficult as the amount of complexing $BaTiO_3$ increases. The microstructures and the electrical properties of the thin films were gen-erally improved with the incease of the heating temperature. However the presence of the pyrochlore phase could not be removed effectively. Our study showed that the electrical properties of $Bi_4Ti_3O_{12}{\cdot}BaTiO_3$ were pronouncedly improved with complexing with BaTiO3 when compared to those of $Bi_4Ti_3O_{12}$ while the presence of the pyrochlore phase was detrimental to the those of $Bi_4Ti_3O_{12}{\cdot}2BaTiO_3$.

• Journal of the Korean Vacuum Society
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• v.9 no.4
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• pp.373-378
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• 2000

There was a great difference in the formation kinetics of $TiO_2$ and $Bi_2O_3$ on silicon, but the growth of bismuth titanate (BIT) thin film was mainly limited by the formation of $TiO_2$. As a result, the BIT film was easy to be lack of bismuth. The pulse injection metalorganic chemical vapor deposition (MOCVD) process was introduced in order to overcome this problem by recovering the insufficient bismuth content in the film. By this pulse injection method, bismuth content was increased and also the uniform in-depth composition of the film was attained with a abrupt $Bi_4Ti_3O_{12}/Si$ interface. In addition, the crystallinity of $Bi_4Ti_3O_{12}$ thin film prepared by pulse injection process was greatly improved and the leakage current density was lowered by 1/2~1/3 of magnitude. Clockwise hysteresis of C-V was observed and the ferroelectric switching was confirmed for $Bi_4Ti_3O_{12}$ film deposited by pulse injection method.

• Journal of the Korean Ceramic Society
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• v.38 no.6
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• pp.558-567
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• 2001

본 연구에서는 알콕사이드를 전구물질로 하는 졸겔공정을 이용하여 Bi 과잉 12 mol%의 조성인 B $i_4$ $Ti_3$ $O_{12}$ 박막과 B $i_4$ $Ti_{3-x}$T $a_{x}$ $O_{12}$(x=0.1, 0.2, 0.3) 박막을 제조하였다. XPS 분석에 따르면 Ta 치환 x=0.2에서 Bi 4f의 photoemission 곡선이 낮은 결합에너지로 이동하였고 피크 강도가 감소하는 현상이 관측되었다. 이는 x=0.1과 0.2 사이에서 Bi-O 결합이 길어져 인장상태 하에 있었음을 나타내었다. B $i_4$ $Ti_3$ $O_{12}$(BIT) 박막의 유전상수와 유전손실은 100 kHz에서 340, 0.05이었고, B $i_4$ $Ti_{3-x}$T $a_{x}$ $O_{12}$ 박막에서 이들 값은 x=0.1에서 가장 높았으며, 각각 480, 0.13이었다. B $i_4$ $Ti_3$ $O_{12}$ 박막의 잔류분극과 항전계는 1.24$\mu$C/$ extrm{cm}^2$, 31.4 kV/cm 이었으나, Ta 치환 x=0.2에서 이들 값은 각각 19.7$\mu$C/$\textrm{cm}^2$, 49.5 kV/cm 에 이르렀다. 또한, B $i_4$ $Ti_3$ $O_{12}$ 박막의 누설전류 밀도는 ~$10^{-6}$ A/$\textrm{cm}^2$ 정도이었으며, Ta 치환은 누설전류를 감소시켜 Ta 치환 x=0.2 이상에서 BIT 박막에 비해 한 차수 정도 낮아졌다. Ta 치환에 따른 B $i_4$ $Ti_3$ $O_{12}$ 전기 물성에서 변화는 Bi-O 결합에서 관측된 인장상태로의 전이와 연관성이 있었으며, 덧붙여 치환에서 생성된 전자에 의한 정공보상이 이에 영향을 끼쳤다. 정공보상이 이에 영향을 끼쳤다.끼쳤다.

• The Transactions of The Korean Institute of Electrical Engineers
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• v.67 no.4
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• pp.543-548
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• 2018

Ferroelectric $Bi_4Ti_3O_{12}$ films were deposited on $SrTiO_3(100)$ and Si(100) substrate by using conductive $SrRuO_3$ films as underlayer, and their ferroelectric and electrical properties were investigated depending on crystal structure and orientation. C-axis oriented $Bi_4Ti_3O_{12}$ films were grown on well lattice-matched pseudo-cubic $SrRuO_3$ films deposited on $SrTiO_3(100)$ substrate, while random-oriented polycrystalline $Bi_4Ti_3O_{12}$ films were grown on $SrRuO_3$ films deposited on Si(100) substrate. The random-oriented polycrystalline film showed a good ferroelectric hysteresis property with remanent polarization ($P_r$) of $9.4{\mu}C/cm^2$ and coercive field ($E_c$) of 84.9 kV/cm, while the c-axis oriented film showed $P_r=0.64{\mu}C/cm^2$ and $E_c=47kV/cm$ in polarizaion vs electric field curve. The c-axis oriented $Bi_4Ti_3O_{12}$ film showed a dielectric constant of about 150 and lower thickness dependence in dielectric constant compared to the random-oriented film. Furthermore, the c-axis oriented $Bi_4Ti_3O_{12}$ film showed leakage current lower than that of the polycrystalline film. The difference of ferroelectric properties in two films was explained from the viewpoint of depolarization effect due to orientation of spontaneous polarization and layered crystal structure of bismuth-base ferroelectric oxide.

• Proceedings of the Korean Institute of Electrical and Electronic Material Engineers Conference
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• 2005.11a
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• pp.236-237
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• 2005

The structural properties of $(Bi,Ce)_4Ti_3O_{12}(BCT)$ thin films with post-annealing temperature were investigated. $(Bi,Ce)_4Ti_3O_{12}(BCT)$ thin films were deposited by RF sputtering method on Pt/Ti/$SiO_2$/Si substrates with optimum deposition condition. The $(Bi,Ce)_4Ti_3O_{12}(BCT)$ thin films was post-annealed at 600$^{\circ}C$, 650$^{\circ}C$, 700$^{\circ}C$, 750$^{\circ}C$, 800$^{\circ}C$ in furnace,respectively. Increasing the post-annealing temperature, the grain size, density and peak intensity of (117) and c-axis orientation were increased. The $(Bi,Ce)_4Ti_3O_{12}(BCT)$ thin films that annealed at 750$^{\circ}C$ exhibited well crystallized phase and had no vacancy and grain was uniform. but there are some secondary phases observed. At this time, the average thickness of $(Bi,Ce)_4Ti_3O_{12}(BCT)$ thin films was 2000 ${\AA}$.

• Journal of the Korean Crystal Growth and Crystal Technology
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• v.23 no.1
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• pp.14-19
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• 2013

We have successfully synthesized $Bi_{4-x}La_xTi_3O_{12}$ (x~2) having Aurivillius-type layered perovskite structure from exfoliated layered perovskite oxide of $K_2La_2Ti_3O_{10}$ with Ruddlesden-Popper structure. The reaction between the exfoliated lanthanum titanate nanosheets and BiOCl nanocrystal resulted in the formation of polycrystalline $Bi_{4-x}La_xTi_3O_{12}$ (x~2) after heating above $700^{\circ}C$. Colloidal suspension of the nanosheets could be obtained by intercalating ethylamine (EA) into the protonated lanthanum titanate, $H_2La_2Ti_3O_{10}$, derived from $K_2La_2Ti_3O_{10}$. Transmission electron microscopic (TEM) analysis show that the exfoliated lanthanium titanate nanosheets have a thickness of a few nano meters. According to X-ray diffraction (XRD) analysis, the exfoliated lanthanium titanate was found to be transformed into $Bi_{4-x}La_xTi_3O_{12}$ (x~2) after restacking with BiOCl and subsequent thermal treatment at > $700^{\circ}C$.

• Proceedings of the Korean Vacuum Society Conference
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• 2000.02a
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• pp.103-103
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• 2000

강한 결정 방향 의존성과 낮은 항정계를 갖는 Bi4Ti3O12 강유전체 박막은 NDRO형 비휘발성 강유전체 메모리 분야에서 매우 유망한 재료이다. 이를 위해서는 실리콘 기판과의 계면조절과 실리콘 기판성에서 고품질의 강유전성 박막을 성장시키는 기술이 필수적이다. MOCVD에 의한 Bi4Ti3O12 의 증착에서는 Bi 성분의 강한 휘발 특성과 낮은 반응성으로 인하여 조성과 두께 등의 조절이 매우 어렵다. 따라서 화학기상증착의 기구를 이해하고 제어하는 기술이 양질의 박막을 얻는데 필수적이다. 본 연구에서는 유기금속 원료 TPB, TIP 과 산소를 이용하여 실리콘 기판위에 Bi4Ti3O12 강유전체 박막을 증착할 때, 증착 변수의 변화에 따른 박막의 증착 거동과 구조적, 전기적 특성을 연계하여 분석하였다. 특히 기판부착력이 낮고 휘발성이 강한 Bi의 특성으로 인한 문제를 개선하기 위하여 TIP원료를 주기적으로 공급, 중단을 반복하는 펄스주입법을 고안하여 그 효과를 살펴보았다. 실리콘 기판위에서 TiO2의 증착속도는 실험온도 영역에서 온도에 따라 변화하지 않는 전형적인 물질 전달에 의해 지배되는 양상을 나타내었다. 반면 Bi2O3 경우에는 50$0^{\circ}C$ 이상에서 급격하게 증착속도가 감소하는 특이한 경향을 나타내었으며 이는 Bi2O3의 높은 휘발성 때문일 것이다. Bi4Ti3O12 박막은 온도증가에 따라 증착속도가 증가한 후 $600^{\circ}C$ 이상에서 포화되는 경향을 보였다. 이로부터 실리콘 기판위에서의 Bi4Ti3O12 박막의 증착 모델을 제시하였다. Bi2O3에 비해 상대적으로 표면 부착력이 월등히 큰 TiO2가 우선적으로 실리콘 펴면에 형성된 후 TPB 유기금속 원료가 이 TiO2와 반응하는 과정으로 Bi4Ti3O12 박막이 증착된다. $600^{\circ}C$이상에서는 증착 변수들을 바꾸어도 물성이 변하지 않는 자기조절기능이 있음을 알 수 있었는데 이는 고온에서의 Bi2O3의 강한 휘발성 때문일 것이다. 실리콘 기판에서 층상 페로브스카이트 상은 58$0^{\circ}C$ 이상에서 형성되며, 매우 좁은 온도 변화에도 결정구조, 박막현상 및 성분이 크게 바뀌는 온도에 민감한 증착거동이 관찰되었다. 증착 모델에서 예견되는 Bi의 불리함을 개선하기 위해 펄스주입법을 실시한 경우 Bi의 성분량이 증가되었고 결정성이 향상되었다. 이로부터 펄스주입법이 박막내에 부족하기 쉬운 Bi를 보충하여 박막의 특성을 개선함을 확인하였다. Bi4Ti3O12 박막의 증착온도에 따른 누설전류 특성 측정 결과 증착온도가 감소할수록 누설전류가 감소함을 알 수 있었고 펄스주입법이 연속주입법보다 더 낮은 누설전류를 보임을 알았다. 펄스주입법의 경우 -2.5V 인가 시의 누설전류는 7.4$\times$10-8A/cm2에서 1.3$\times$10+7A/cm2의 매우 우수한 값을 가졌다. 연속 주입법에 의해 증착된 박막은 C-V 측정 결과 강유전성 이력이 나타나지 않았으나, $600^{\circ}C$ 이상에서 펄스주입법에 의해 증착된 박박은 강유전성 이력을 나타내었다.

• Korean Journal of Crystallography
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• v.5 no.2
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• pp.85-92
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• 1994

Ferroelectric Bi4Ti3012 thin films have been grown on LaAlO(001) by Pulsed-laser deposition. Phase formation and structural films prepared of the films prepared at varigus deposition temperatures are investigated using x-ray diffraction The film grown at 740℃ shows epitaxial growth behavior with c-akis normal to the substrate. N2tBmstiucCures of Bi4Ti3012/YBa2Cu307-x/LaAIO3(001) have been in-situ grown. Even though the a-and b-axes of the Yba2Cu307-x layer show epitaxial growth behavior.

• The Korean Journal of Ceramics
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• v.4 no.1
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• pp.33-36
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• 1998

Epitaxially grown $Bi_4Ti_3O_{12}$ thin films on the MgO(100) substrates was prepared by dipping-pyrolysis process using metal naphthenates as starting materials. The films annealed at various temperatures were charactrized by X-ray diffraction $\theta$-2$\theta$ scans and pole-figure analysis ($\beta$ scanning). Highly c-axia oriented Bi4Ti3O12 films were crystallized by heat-treatment at 700$^{\circ}$ and 75$0^{\circ}C$ from precursor films pyrolyzed at 50$0^{\circ}C$. The X-ray pole-figure analysis indicated that the $Bi_4Ti_3O_{12}$ thin films have an epitaxial relationship with the MgO(100) substrates.

• Journal of the Korean Ceramic Society
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• v.35 no.9
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• pp.1002-1005
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• 1998

Bismuth titanate thin films were prepared on {{{{ { SrTiO}_{3 } }}(100) and Si(100) substrates by dipping-pyrolysis pro-cess using metal naphthenates as starting materials. crystallinity and in-phase alignment of the films were analyzed by X-ray diffraction $\theta$-2$\theta$ scans and $\beta$ scans (pole-figures) respectively. Highly c-axis-oriented {{{{ { { {Bi }_{4 }Ti }_{3 }O }_{12 } }} thin films with smooth surfaces were obtained after heat treatment at 75$0^{\circ}C$ on {{{{ { SrTiO}_{3 } }}(100) sub-strate while the films grown of Si(100) exhibited polycrstalline characteristics. C-axis oriented film show-ed an epitaxial relationship with the {{{{ { SrTiO}_{3 } }} substrate.