• Proceedings of the Korean Institute of Electrical and Electronic Material Engineers Conference
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• 2007.06a
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• pp.277-277
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• 2007

$(Bi,La)_4Ti_3O_{12}$ (BLT) 물질은 결정 방향에 따른 강한 이방성의 강유전 특성을 나타낸다. 따라서 BLT 박막을 이용하여 FeRAM 소자 등을 제작하기 위해서는 결정의 방향성을 세심하게 제어하는 것이 매우 중요하다. 현재까지 연구된 BLT 박막의 방향성 조절 결과를 보면, BLT 박막을 스핀 코팅 법 (spin coating method)으로 중착하고, 핵생성 열처리 단계를 조절하여 무작위 방향성 (random orientation)을 갖는 박막을 제조하는 방법이 일반적이었다. 그런데 이러한 스핀 코팅법에서의 핵생성 단계의 제어는 공정 조건 확보가 너무 어려운 단점이 있다. 이러한 어려움을 극복할 수 있는 대안은 스퍼터링 증착법 (sputtering deposition method), PLD법 (pulsed laser deposition method) 등과 같은 PVD (physical vapor deposition) 법의 증착방법을 적용하는 것이다. PVD 법으로 증착하는 경우에는 이미 박막 내에 무수한 결정핵이 존재하기 때문에 핵생성 단계가 필요 없게 된다. PVD 증착법의 적용을 위해서는 타겟 (target)의 제조 및 평가 실험이 선행되어야 한다. 그런데 벌크 BLT 재료의 소결공정 조건과 전기적 특성에 관한 연구 결과는 거의 발표 되지 않고 있다. 본 실험에서는 $Bi_2O_3$, $TiO_2$ and $La_2O_3$ 분말을 이용하여 최적의 조성을 구하기 위하여 Bi양을 변화시키며 타겟을 제조 하였다. 혼합된 분말을 하소 후 pallet 형태로 성형하여 소결을 실시하였다. 시편을 1mm 두께로 연마하고, 표면에 silver 전극을 인쇄하여 전기적 특성을 측정하였다. Bi양이 3.28몰 첨가된 조성에서 최대의 잔류분극 (2Pr) 값을 얻었고, 이때의 값은 약 $18{\mu}C/cm^2$ 정도였다. 최적화된 조성 ($Bi_{3.28}La_{0.75}Ti_3O_{12}$)으로 BLT 타겟을 제조하여 PLD법으로 박막을 제조하였다. 박막 제조 시 압력은 $1{\times}10^{-1}\;{\sim}\;1{\times}10^{-4}\;Torr$ 범위에서 변화시켰다. $1{\times}10^{-1}\;Torr$ 압력을 제외하고는 모든 압력에서 BLT 박막이 증착되었다. 중착된 박막을 $650\;{\sim}\;800^{\circ}C$에서 30분간 열처리를 실시하고 전기적 특성을 평가한 결과, $1{\times}10^{-2}\;Torr$에서 증착한 박막에서 양호한 P-V (polarization-voltage) 이력곡선을 얻을 수 있었고, 이때의 잔류분극 (2Pr) 값은 약 $6\;{\mu}C/cm^2$ 이었다. 주사전자현미경 (SEM)을 이용하여 BLT 박막 표면의 미세구조도 관찰하였는데, 스핀코팅 법으로 증착한 경우에 관찰되었던 조대화된 입자들은 관찰되지 않았고, 상당히 양호한 입자 크기 균일도를 나타내었다.

• Proceedings of the Korean Institute of Electrical and Electronic Material Engineers Conference
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• 2007.11a
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• pp.279-279
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• 2007

비휘발성 메모리 Fe-RAM은 빠른 정보처리 속도와 전원공급이 차단되었을 때도 계속 정보를 유지할 수 있는 비휘발성 특징과 더불어 저전압, 저전력 구동의 장점이 있어서, 차세대 메모리로 많은 주목을 받고 있다. FeRAM에 사용되는 강유전체는 주로 Pb(Zr,Ti)$O_3$가 적용되었는데, 최근에는 비납계 강유전체의 연구도 활발히 이루어지고 있다. 이러한 비납계 강유전체 중에서 가장 특성이 우수한 물질은 $(Bi,La)_4Ti_3O_{12}$ (BLT) 이다. 그런데 BLT는 결정 방향에 따른 강한 이방성의 강유전 특성을 나타내기 때문에 BLT 박막을 이용하여 Fe-RAM 소자 등을 제작하기 위해서는 결정의 방향성을 세심하게 제어하는 것이 매우 중요하다. 지금까지 연구된 BLT 박막의 방향성 조절결과를 보면, BLT 박막을 스핀 코팅 법 (spin coating method)으로 증착하고, 핵생성 열처리 단계를 조절하여 무작위 방향성을 갖는 박막을 제조하는 방법이 일반적이었다. 그런데 이러한 스핀 코팅법에서의 핵생성 단계의 제어는 공정 조건 확보가 너무 어려운 단점이 있다. 이러한 어려움을 극복할 수 있는 대안은 스퍼터링 증착법(sputtering deposition method), PLD (pulsed laser deposition)법 등과 같은 PVD (physical vapor deposition) 법의 증착방법을 적용하는 것이다. PVD 법으로 증착하는 경우에는 이미 박막 내에 무수한 결정핵이 존재하기 때문에 핵생성 단계가 필요가 없게 된다. PVD 증착법의 적용을 위해서는 타겟의 제조 및 평가 실험이 선행되어야 한다. 그런데 벌크 BLT 재료의 소결공정 조건과 전기적 특성에 관한 연구 결과는 거의 발표가 되지 않고 있다. 본 실험에서는 $Bi_2O_3,\;TiO_2,\;La_2O_3,\;Nb_2O_5\;and\;Al_2O_3$ 분말들을 이용하여 최적의 조성을 구하기 위하여 $Nb^{+5}$ 와 $Al^{+3}$을 $Ti^{+4}$ 자리에 소량 치환시켜 제조하였다. 혼합된 분말을 하소 후 pellet 형태로 성형하여 소결을 실시하였다. 시편을 1mm 두께로 연마하고, 양면에 silver 전극을 인쇄하여 전기적 특성을 측정하였다. 측정결과 $Ti^{+4}$ 자리에 $Nb^{+5}$를 치환하여 제조한 시편에서 $2P_r{\sim}31\;{\mu}c/cm^2$정도의 매우 우수한 특성을 얻었다.

• Proceedings of the Korean Institute of Electrical and Electronic Material Engineers Conference
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• 2006.11a
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• pp.192-193
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• 2006

A 16Mb ITIC FeRAM device was fabricated with BLT capacitors. The average value of the switchable 2 polarization obtained m the 32k-array (unit capacitor size: 068 ${mu}m^2$) capacitors was about 16 ${\mu}C/cm^2$ at 3V and the uniformity within an 8-inch wafer was about 2.8%. But a lot of cells were failed randomly during the measuring the bit-line signal of each cell. It was revealed that the Grain size and orientation of the BLT thin film were severely non-uniform. Therefore, the uniformity of the grain size and orientation was improved by changing the process conditions of post heat treatment. The temperature of nucleation step was the very effective on varying the microstructure of the BLT thin film. The optimized temperature of the nucleation step was $560^{\circ}C$.

• Journal of the Korean Institute of Electrical and Electronic Material Engineers
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• v.18 no.5
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• pp.439-444
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• 2005

We investigated the structural and electrical properties of BLT films grown on Si covered with $ZrO_{2}$ buffer layer. The BLT thin film and $ZrO_{2}$ buffer layer were fabricated using a metalorganic decomposition method. The electrical properties of the MFIS structure were investigated by varying thickness of the $ZrO_{2}$ layer. AES and TEM show no interdiffusion and reaction that suppressed using the $ZrO_{2}$ film as a buffer layer The width of the memory window in the C-V curves for the MFIS structure decreased with increasing thickness of the $ZrO_{2}$ layer. It is considered that the memory window width of MFIS is not affected by remanent polarization. Leakage current density decreased by about four orders of magnitude after using $ZrO_{2}$ buffer layer. The results show that the $ZrO_{2}$ buffer layers are prospective candidates for applications in MFIS-FET memory devices.

• Proceedings of the Korean Institute of Electrical and Electronic Material Engineers Conference
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• 2001.11a
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• pp.463-466
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• 2001

In recent year, Ferroelectric BLT($Bi_{4-x}$La$_{x}$Ti$_3$O$_{12}$) is a promising candidate materials. This study was Practiced to make good conditions of BLT targets. In this study, calcination and sintering temperature were kept at 75$0^{\circ}C$, 110$0^{\circ}C$ for 2 hour respectively. the density obtained 7.612, 7.98, 7.877 g/㎤ as La$_2$O$_3$ contents were 0.0mol%, 0.25mo1%, 0.5mol%. Especially, the lanthanum content of 0.5 mol% measured C-axis (117) preferred orientation more than the others targets in the XRD. In $\varepsilon$$_{r}$-f relationship using by HP 4194 A impedance analyzer, the 0.5 mol% observed above 200 relative dielectric constant. but the dissipation factor was higher than others targets at 100Hz~13MHz range. SEM photograph with the content of La$_2$O$_3$ was observed like rod and plate types.types.s.

• Proceedings of the Korean Institute of Electrical and Electronic Material Engineers Conference
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• 2006.06a
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• pp.276-277
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• 2006

1mm-thick BLT ceramics were sintered in accordance with a bulk ceramic fabrication process. AII XRD peaks detected in the sintered ceramics were indexed as the Bi-layered perovskite structure without secondary phases. Density was increased with increasing the sintering temperature up to $1050^{\circ}C$ and the maximum value was about 98% of the theoretical density. The remanent polarization (2Pr) value of BLT ceramic sintered at $1050^{\circ}C$ was approximately $6.5\;{\mu}C/cm^2$ at the applied voltage of 4.5 kV. The calculated electromechanical coupling factor ($k_t$) of it was about 5% and the mechanical quality factor (Qm) was about 2200. From these results, a BLT ceramic target for pulsed laser deposition (PLD) system was successfully fabricated.

• Journal of the Korean Institute of Electrical and Electronic Material Engineers
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• v.20 no.7
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• pp.575-580
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• 2007

A 16 Mb 1T1C FeRAM device was integrated with BLT capacitors. But a lot of cells were failed randomly during the measuring the bit-line signal distribution of each cell. The reason was revealed that the grain size and orientation of the BLT thin film were severely non-uniform. And the grain size and orientation were severely affected by the process conditions of post heat treatment, especially nucleation step. The optimized annealing temperature at the nucleation step was $560^{\circ}C$. The microstructure of the BLT thin film was also varied by the annealing time at the step. The longer process time showed the finer grain size. Therefore, the uniformity of the grain size and orientation could be improved by changing the process conditions of the nucleation step. The FeRAM device without random bit-fail cell was successfully fabricated with the optimized BLT capacitor and the sensing margin in bit-line signal distribution of it was about 340 mV.

• Journal of the Korean Institute of Electrical and Electronic Material Engineers
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• v.16 no.5
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• pp.378-384
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• 2003

Etching species in CF$_4$/Ar plasma and the behavior of etching rate of Bi$_4$-$_{x}$L$_{x}$rTi$_3$O$_2$ (BLT) films were investigated in inductively coupled plasma (ICP) reactor in terms of etch parameters. The etching rate as functions of CF$_4$ contents showed the maximum 803 $\AA$/min at 20% CF$_4$ addition in CF$_4$/Ar plasma. The increase of RF power and DC bias voltage caused to an increase of etch rate. The variation of relative volume densities for F and he atoms were measured with the optical emission spectroscopy (OES). The chemical states of BLT were investigated with using X-ray photoelectron spectroscopy (XPS). XPS narrow scan analysis shows that La-fluorides remained on the etched surface. The presence of maximum etch rate at CF$_4$(20%)/Ar(80%) may be explained by the concurrence of two etching mechanisms such as physical sputtering and chemical reaction. The roles of he ion bombardment include destruction of metal (Bi, La, Ti)-O bonds as well as assistant for chemical reaction of metals with fluorine atoms.oms.

• Proceedings of the Korean Society of Precision Engineering Conference
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• 2010.11a
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• pp.275-276
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• 2010

• Proceedings of the Korean Institute of Electrical and Electronic Material Engineers Conference
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• 2001.11b
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• pp.463-466
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• 2001

In recent year, Ferroelectric $BLT(Bi_{4-x}La_{x}Ti_{3}O_{12})$ is a promising candidate materials. This study was practiced to make good conditions of BL T targets. In this study, calcination and sintering temperature were kept at $750^{\circ}C$, $1100^{\circ}C$ for 2 hour respectively. the density obtained 7.612, 7.98, $7.877g/cm^{3}$ as $La_{2}O_{3}$ contents were 0.0mol%, 0.25mol%, 0.5mol%. Especially, the lanthanum content of 0.5 mol% measured C-axis (117) preferred orientation more than the others targets in the XRD. In $\varepsilon_{r}-f$ relationship using by HP 4194 A impedance analyzer, the 0.5 mol% observed above 200 relative dielectric constant. but the dissipation factor was higher than others targets at 100Hz~13MHz range. SEM photograph with the content of $La_{2}O_{3}$ was observed like rod and plate types.