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Atomic Layer Deposition of ZrSiO4 and HfSiO4 Thin Films using a newly designed DNS-Zr and DNS-Hf bimetallic precursors for high-performance logic devices (DNS-Zr과 DNS-Hf 바이메탈 전구체를 이용한 Gate Dielectric용 ZrSiO4 및 HfSiO4 원자층 증착법에 관한 연구)

  • Kim, Da-Yeong
    • Proceedings of the Korean Institute of Surface Engineering Conference
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    • 2017.05a
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    • pp.138-138
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    • 2017
  • 차세대 CMOS 소자의 지속적인 고직접화를 위해서는 높은 gate capacitance와 낮은 gate leakage current를 확보를 위한, 적절한 metal gate electrode와 high-k dielectric 물질의 개발이 필수적으로 요구된다. 특히, gate dielectric으로 적용하기 위한 다양한 high-k dielectric 물질 후보군 중에서, 높은 dielectric constant와, 낮은 leakage current, 그리고 Si과의 우수한 열적 안정성을 가지는 Zr silicates 또는 Hf silicates(ZrSiO4와 HfSiO4) 물질이 높은 관심을 받고 있으며, 이를 원자층 증착법을 통해 구현하기 위한 노력들이 있어왔다. 그러나, 현재까지 보고된 원자층 증착법을 이용한 Zr silicates 및 Hf silicates 공정의 경우, 개별적인 Zr(또는 Hf)과 Si precursor를 이용하여 ZrO2(또는 HfO2)과 SiO2를 반복적으로 증착하는 방식으로 Zr silicates 또는 Hf silicates를 형성하고 있어, 전체 공정이 매우 복잡해지는 문제점 뿐 아니라, gate dielectric 내에서 Zr과 Si의 국부적인 조성 불균일성을 야기하여, 제작된 소자의 신뢰성을 떨어뜨리는 문제점을 나타내왔다. 따라서, 본 연구에서는 이러한 문제점을 개선하기 위하여, 하나의 precursor에 Zr (또는 Hf)과 Si 원소를 동시에 가지고 있는 DNS-Zr과 DNS-Hf bimetallic precursor를 이용하여 새로운 ZrSiO4와 HfSiO4 ALD 공정을 개발하고, 그 특성을 살펴보고자 하였다. H2O와 O3을 reactant로 사용한 원자층 증착법 공정을 통하여, Zr:Si 또는 Hf:Si의 화학양론적 비율이 항상 일정한 ZrSiO4와 HfSiO4 박막을 형성할 수 있었으며, 이들의 전기적 특성 평가를 진행하였으며, dielectric constant 및 leakage current 측면에서 우수한 특성을 나타냄을 확인할 수 있었다. 이러한 결과를 바탕으로, bimetallic 전구체를 이용한 ALD 공정은 차세대 고성능 논리회로의 게이트 유전물질에 응용이 가능할 것으로 판단된다.

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Deposition mechanism of $Bi_4Ti_3O_{12}$ films on Si by MOCVD and property improvement by pulse injection method (MOCVD $Bi_4Ti_3O_{12}$ 박막의 실리콘 위에서의 증착기구 및 유기 금속원료의 펄스주입법에 의한 박막 특성 개선)

  • 이석규;김준형;최두현;황민욱;엄명윤;김윤해;김진용;김형준
    • 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.

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The Effects of Alkali Sulfate on the Hydration of a C3A−CaSO4⋅2H2O System

  • Lee, Jong-Kyu;Chu, Yong-Sik;Kwon, Choon-Woo
    • Journal of the Korean Ceramic Society
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    • v.44 no.9
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    • pp.471-476
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    • 2007
  • The hydration mechanism of the $3CaO{\cdot}Al_2O_3-CaSO_4{\cdot}2H_2O$ system in the presence of alkali sulfates has been investigated. The early hydration rate of $3CaO{\cdot}Al_2O_3$ was accelerated by the addition of $Na_2SO_4$ and $K_2SO_4$. This is closely related to the formation of syngenite $(CaSO_4{\cdot}K_2SO_4{\cdot}H_2O)$, and the U-phase added $K_2SO_4$ and $Na_SO_4$ in the $3CaO{\cdot}Al_2O_3-CaSO_4{\cdot}2H_2O$ system, respectively. The formation of the rigid syngenite and U-phase structure led to rapid setting and decreases the sulfate content in the liquid phase of the hydrating cement to the extent that it cannot adequately retard the hydration of $3CaO{\cdot}Al_2O_3$. In case of the alkali sulfate not added to the $3CaO{\cdot}Al_2O_3-CaSO_4{\cdot}2H_2O$ system, the ettringite was transformed to monosulfoaluminate immediately after the consumption of gypsum. However, when the alkali sulfates were added to this system, the ettringite did not transform to monosulfoaluminate immediately even though the gypsum was completely consumed. There was a stagnation period to transform to the monosufoaluminate after the consumption of gypsum because the syngenite and U-phase remained as the sulfate source.

Synthesis of Li2MnSiO4 by Solid-state Reaction (고상반응법을 이용한 Li2MnSiO4 합성)

  • Kim, Ji-Su;Shim, Joong-Pyo;Park, Gyung-Se;Sun, Ho-Jung
    • Journal of the Korean Institute of Electrical and Electronic Material Engineers
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    • v.25 no.5
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    • pp.398-402
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    • 2012
  • Synthesis of $Li_2MnSiO_4$ was attempted by the conventional solid-state reaction method, and the phase formation behavior according to the change of the calcination condition was investigated. When the mixture of the three source materials, $Li_2O$, MnO and $SiO_2$ powders, were used for calcination in air, it was difficult to develop the $Li_2MnSiO_4$ phase because the oxidation number of $Mn^{2+}$ could not be maintained. Therefore, two-step calcination was applied: $Li_2SiO_3$ was made from $Li_2O$ and $SiO_2$ at the first step, and $Li_2MnSiO_4$ was synthesized from $Li_2SiO_3$ and MnO at the second step. It was easy to make $Li_2MnSiO_3$ from $Li_2O$ and $SiO_2$. $Li_2MnSiO_4$ single phase was developed by the calcination at $900^{\circ}C$ for 24 hr in Ar atmosphere as the oxidation of $Mn^{2+}$ was prevented. However, the $Li_2MnSiO_4$ was ${\gamma}-Li_2MnSiO_4$, one of the polymorph of $Li_2MnSiO_4$, which could not be used as the cathode materials in Li-ion batteries. By applying the additional low temperature annealing at $400^{\circ}C$, the single phase ${\beta}-Li_2MnSiO_4$ powder was synthesized successfully through the phase transition from ${\gamma}$ to ${\beta}$ phase.

Single-crystal Structure of Fully Dehydrated and Largely NH4+-exchanged Zeolite Y (FAU, Si/Al = 1.70), │(NH4)60Na11│[Si121Al71O384]-FAU

  • Seo, Sung-Man;Kim, Ghyung-Hwa;Kim, Young-Hun;Wang, Lian-Zhou;Lu, Gao-Qing;Lim, Woo-Taik
    • Bulletin of the Korean Chemical Society
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    • v.30 no.3
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    • pp.543-550
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    • 2009
  • The single-crystal structure of largely ammonium-exchanged zeolite Y dehydrated at room temperature (293 K) and 1 ${\times}\;10^{-6}$ Torr. has been determined using synchrotron X-radiation in the cubic space group $Fd\overline{3}m\;(a=24.9639(2)\AA)$ at 294 K. The structure was refined to the final error index $R_1$ = 0.0429 with 926 reflections where $F_o>4\sigma(F_o)$; the composition (best integers) was identified as |$(NH_4)_{60}Na_{11}$|[$Si_{121}Al_{71}O_{384}$]-FAU. The 11 $Na^{+}$ ions per unit cell were found at three different crystallographic sites and 60 ${NH_4}^{+}$ ions were distributed over three sites. The 3 $Na^{+}$ ions were located at site I, the center of the hexagonal prism ($Na-O\;=\;2.842(5)\;\AA\;and\;O-Na-O\;=\;85.98(12)^{\circ}$). The 4 $Na^{+}$ and 22 ${NH_4}^{+}$ ions were found at site I' in the sodalite cavity opposite the double 6-rings, respectively ($Na-O\;=\;2.53(13)\;\AA,\;O-Na-O\;=\;99.9(7)^{\circ},\;N-O\;=\;2.762(11)\;\AA,\;and\;O-N-O =\;89.1(5)^{\circ}$). About 4 $Na^{+}$ ions occupied site II ($(Na-O\;=\;2.40(4)\;\AA\;and\;O-Na-O\;=\;108.9(3)^{\circ}$) and 29 ${NH_4}^{+}$ ions occupy site II ($N-O\;=\;2.824(9)\;\AA\;and\;O-N-O\;=\;87.3(3)^{\circ}$) opposite to the single 6-rings in the supercage. The remaining 9 ${NH_4}^{+}$ ions were distributed over site III' ($N-O\;=\;2.55(3),\;2.725(13)\;\AA\;and\;O-N-O\;=\;94.1(13),\;62.16(15),\;155.7(14)^{\circ}$).

Effect of ${Gd_2}{O_3}$ Addition on the Sintered Density and Resintered Density in <${UO_2}-{Gd_2}{O_3}$ Pellets (${UO_2}-{Gd_2}{O_3}$소결체에서 ${Gd_2}{O_3}$첨가가 소결 및 재소결밀도에 미치는 영향)

  • Baek, Jong-Hyeok
    • Korean Journal of Materials Research
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    • v.5 no.3
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    • pp.364-370
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    • 1995
  • ex-AUC U$O_{2}$ 분말과 $Gd_{2}$O_{3}$ 분말을 기계적으로 혼합하여 소결한 U$O_{2}$-$Gd_{2}$O_{3}$ 소결체의 밀도 변화와 재소결 후 밀도변화를 기공크기 및 분포의 변화로 서술하였다. 수소분위기에서 175$0^{\circ}C$, 4시간 동안 소결하였을 때, 순수 U$O_{2}$의 소결밀도는 97.2% T.D.였으나 6wt% $Gd_{2}$O_{3}$ 첨가까지는 U$O_{2}$-$Gd_{2}$O_{3}$의 소결밀도는 $U^{+4}$와 $Gd^{+4}$의 상호확산 때문에 약 90% T.D.로 급격히 감소하였다. 그러나 6wt% 이상의 $Gd_{2}$O_{3}$가 첨가되면 우라늄이온 산화아와 산소침입으로 인하여 소결밀도는 오히려 증가하였다. 1$700^{\circ}C$에서 재소결시킬 때 순수 U$O_{2}$ 소결체에서는 재소결 시간에 따라 밀도증가가 발생하였다. U$O_{2}$-$Gd_{2}$O_{3}$ 소결체 경우에는 재소결시 밀도가 감소하였으나 재소결 시간이 증가함에 따라 다시 밀도는 증가하였고, 6wt%$Gd_{2}$O_{3}$가 첨가된 U$O_{2}$-$Gd_{2}$O_{3}$ 소결체에서 밀도가 가장 많이 감소하였다.

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A Study on the Constituents from the Roots of Polygala tenuifolia (원지(Polygala tenuifolia WILLD.) 뿌리의 성분연구)

  • Lee, Young-Sun;Lee, Je-Hyun;Kim, Chung-Sook;Kim, Jin-Sook
    • Korean Journal of Pharmacognosy
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    • v.30 no.2
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    • pp.168-172
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    • 1999
  • Five compounds were isolated from the roots of Polygala tenuifolia (Polygalaceae). On the basis of spectroscopic evidences, the structures of these compounds were characterized as ${\alpha}-D-(6-O-sinapoyl)-glucopyranosyl(1{\rightarrow}2')-{\beta}-D-(3'-O-sinapoyl)-fructofuranoside$ (P3), ${\alpha}$-D-{6-O-(p-methoxybenzoyl)}-glucopyranosyl-$(1{\rightarrow}2')$-${\beta}$-D-{3'-O-(3',4',5'-trimethoxycinnamoyl)}-fructofuranoside(P4), ${\alpha}$-D-{6-O-(p-hydroxybenzoyl)}-glucopyranosyl-$(1{\rightarrow}2')$-${\beta}$-D-{3'-O-(3',4',5'-trimethoxycinnamoyl)}-fructofuranoside(P5), ${\alpha}-D-glucopyranosyl-(1{\rightarrow}2')-{\beta}-D-(1'-O-sinapoyl)-fructofuranoside$(P6), $1,5-anhydro-D-glucitol$(P7) respectively. ${\alpha}$-D-{6-O-(p-Methoxybenzoyl)}-glucopyranosyl-$(1{\rightarrow}2')$-${\beta}$-D-{3'-O-(3',4',5'-trimethoxycinnamoyl)}-fructofuranoside(P4) and ${\alpha}-D-glucopyranosyl-(1{\rightarrow}2')-{\beta}-D-(1'-O-sinapoyl)-fructofuranoside$(P6) were isolated for the first time from the genus of Polygala. 1,5-Anhydro-D-glucitol(P7) was isolated without hydrolysis for the first time from the root of Polygala tenuifolia.

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Low-temperature sintering and dielectric properties of the (1-x)$BiNbO_4-(x)ZnNb_2O_6$ ceramics ((1-x)$BiNbO_4-(x)ZnNb_2O_6$ 세라믹스의 저온 소결 및 유전 특성)

  • Kim, Yun-Han;Yoon, Sang-Ok;Kim, Shin;Kim, Kwan-Soo;Kim, Kyung-Joo;Park, Jong-Guk
    • Proceedings of the Korean Institute of Electrical and Electronic Material Engineers Conference
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    • 2007.11a
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    • pp.284-284
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    • 2007
  • In this study, the microwave dielectric property variations of (1-x)$BiNbO_4-(x)ZnNb_2O_6$ composites (x=0.3, 0.5 and 0.7) with 10wt% zinc borosilicate(ZBS) glass was investigated as a function of the substitution of $ZnNb_2O_6$ with a view to applying thes system to LTCC technology. The all composition addition of 10wt% ZBS glass ensured a successful sintering below $900^{\circ}C$. In addition, a small amount of $Bi_2SiO_5$ as the secondary phase was observed in the all composition. The substitution of $ZnNb_2O_6$ on the $BiNbO_4$ composites increased the $Q{\times}f$ values, but it decreased the sinterability and dielectric constant due to the high sintering temperature and low dielectric constant of $ZnNb_2O_6\;than\;BiNbO_4$ ceramics. The increasing of $ZnNb_2O_6$ content from 0.3 to 0.7 in the (1-x)$BiNbO_4-(x)ZnNb_2O_6$ composites with 10wt% ZBS glass sintered at $900^{\circ}C$ demonstrated 28.1~15.6 in the dielectric constant$({\varepsilon}_r)$, 5,500~8,700GHz in the $Q{\times}f$ value.

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Microwave Dielectric Properties of (1-x)CaTiO3-xYAIO3 and its Low Temperature Densification by CaB2O4 Addition ((1-x)CaTiO3-xYAIO3계의 마이크로파 유전특성과 CaB2O4첨가제의 영향)

  • 강보경;김경용;김범수;김주선;김병호
    • Journal of the Korean Ceramic Society
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    • v.40 no.1
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    • pp.81-86
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    • 2003
  • Microwave dielectric properties have been investigated in the$(1-x)CaTiO_3-xYAlO_3$ (x=0.1~1.0) solid solution system. The mixtures of $CaTiO_3$ and $YalO_3$using solid state method were sintered at various temperatures. Their dielectric constants and related temperature coefficients were strongly depend on the composition of the solid solution. The optimum properties were recorded as for ${\varepsilon}_r=47,$ $Q{\times}f_0$=35000 and ${\tau}_f=+11ppm/^{\circ}C$ without sintering agent. Even at $1200^{\circ}C$ full densification has been achieved with addition of $CaB_2O_4$ in the $0.75CaTiO_3-0.25YalO_3$ composition. The sample of $0.3 wt%-CaB_2O_4$ added $ 0.75CaTiO_3-0.25YalO_3$ sintered at $1300^{\circ}C$ for 3 h showed optimum microwave dielectric properties of ${\varepsilon}_r=47$, $Q{\time}f_0=37000$ and ${\tau}_f=+17ppm/^{\circ}C$, which demonstrates the promising candidates for microwave dielectric materials covering 5~7 GHz range.