• Journal of the Korean Ceramic Society
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• v.32 no.7
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• pp.853-857
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• 1995

ZrSiO4 powders were prepared from partially hydrolyzed solution of Si(OC2H5)4 and ZrOCl2.8H2O solution by the sol-gel method and formation rate of ZrSiO4 on the reaction parameter was investigated. In order to prepare homogeneous ZrSiO4 precursor gels, the H2O/Si(OC2H5)4 molar ratio of about 2, the pH of the ZrOCl2.8H2O solution fo about 4 and stirring time of the mixed solutions of about 2 hrs were appropriate. Formation of temperature of ZrSiO4 reduced about 15$0^{\circ}C$ by milling and formation of ZrSiO4 at 1300~135$0^{\circ}C$ showed an accelerative increase through the hedvall effect by silica.

• 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.

• Applied Chemistry for Engineering
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• v.5 no.6
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• pp.1044-1055
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• 1994

The preparation of ZrC/SiC mixed powders from $ZrSiO_4/C$ and $ZrSiO_4/Al/C$ systems was attempted in the temperature range below $1600^{\circ}C$ under Ar or $Ar/H_2$ gas flow(100-500ml/min). The formation mechanism and kinetics of ZrC/SiC were suggested and the resultant powders were characterized. In $ZrSiO_4/C$ system, ZrC and SiC were formed by competitive reaction of $ZrO_2(s)$ and SiO(g) with carbon at temperature higher than $1400^{\circ}C$. The apparent activation energy for the formation of ZrC was approximately 18.5kcal/mol($1400-1600^{\circ}C$). In $ZrSiO_4/Al/C$ system, ZrC was formed by reaction of ZrO(g) with Al(l, g) and carbon at temperature higher than $1200^{\circ}C$, and SiC was formed by reduction-carbonization of SiO(g) with Al(l, g) and carbon at temperature higher than $1300^{\circ}C$. The products obtained at $1600^{\circ}C$ for 5h consisted of ZrC with lattice constant of $4.679{\AA}$ and crystallite size of $640{\AA}$, and SiC with lattice constant of $4.135{\AA}$ and crystallize size of $500{\AA}$. And also, the mean particle size was about $21.8{\mu}m$.

• Korean Journal of Materials Research
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• v.13 no.9
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• pp.572-580
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• 2003

Synthesizing behavior and microstructural evolution of $CaZrO_3$and $m-ZrO_2$in a thermal reaction process of $ZrSiO_4$-$xCaCO_3$mixtures, where x is 7 and 19, were investigated to determine the addition amount of CaO in CaO:$ZrO_2$:$SiO_2$ternary composition. CaZrO$_3$-Ca$_2$SiO$_4$precursor prepared by the mixture of $ZrSiO_4$and CaCO$_3$in aqueous suspending media was controlled to the acidic (pH=4.0) condition with HCI solution to enhance the thermal reaction. The addition amount of dispersant into the $ZrSiO_4$-$xCaCO_3$slip increased with increasing mole ratio of $CaCO_3$, which was associated with the viscosity of slip. Decarbonation reaction was activated with an increase of the addition amount of $CaCO_3$, showing different final temperatures in $ZrSiO_4$-$7CaCO_3$and $ZrSiO_4$-$19CaCO_3$mixtures as about 980 and 116$0^{\circ}C$, respectively, for finishing decarbonation reaction. The grain morphology was changed to spherical shape for all samples with an increase of sintering temperature. The grain size and phase composition of the synthesized composites depended on the mixture ratio of Zrsi04 and CacO3 powders, indicating that the main crystals were m-ZrO2 ($\leq$3 $\mu\textrm{m}$) and $CaZrO_3$ ($\leq$ 7 $\mu\textrm{m}$) in $ZrSiO_4$$>-7CaCO_3$and $ZrSiO_4$-$19CaCO_3$mixtures, respectively.

• Journal of the Korean Vacuum Society
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• v.9 no.4
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• pp.315-320
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• 2000

We have investigated the crystal structure and electrical properties of Pt/SBT/$ZrO_2$/Si (MFIS) and Pt/SBT/Si (MFS) structures for the gate oxide of ferroelectric memory. XRD spectra and SEM showed that the SBT film of SBT/$ZrO_2$/Si structure had larger grain than that of SBT/Si structure. $ZrO_2$ film between SBT film and Si substrate is confirmed as a good candidate for a diffusion barrier by the analysis of AES. The remanent polarization decreased and coercive voltage increased in Pt/SBT/$ZrO_2$/Pt/$SiO_2$/Si structure. This effect may increase memory window of MFIS structure directly related to the coercive voltage. From the capacitance-volt-age characteristics, the memory windows of Pt/SBT (210 nm)/$ZrO_2$ (28 nm)/Si structure were in the range of 1~l.5 V at the applied voltage of 4~6 V. The current densities of Pt/SBT/ZrO$_2$/Si with as -deposited Pt electrode and annealed at $800^{\circ}C$ in $O_2$ambient were $8\times10^{-8} A/\textrm{cm}^2$ and $4\times10^{-8}A/\textrm{cm}^2$ , respectively.

• Journal of the Korean Ceramic Society
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• v.23 no.4
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• pp.23-26
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• 1986

The synthetic conditions of $ ZrSiO_4-Cd(S_xS_{1-x})$ stains from CdS, Se, $SiO_2$ , 4ZrO_2$ and Lif were investigated and the colors were examined. Colors of the stains prepared were yellow orange red pink ruby and violet in relation to both the content of CdS-Se in $ZrSiO_4$ and firing temperature. Colors of these series stains were thermally stabilized probably by the structural stability of zirconium silicate. Furthermore by the result of X-ray diffraction analysis it is assumed that color of the zircon cadmium sulphoselenide $ ZrSiO_4-Cd(S_xS_{1-x})$ stain is developed by neither the coloring ions in $ZrSiO_4$ lattice nor the solid solution of $ZrSiO_4$ and $Cd(S_xS_{1-x})$ but by the small crystals of $Cd(S_xS_{1-x})$ being occluded by the zirconium silicate during sintering process.

• Journal of the Korean Ceramic Society
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• v.37 no.12
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• pp.1178-1186
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• 2000

타일의 내마모성과 내산성을 향상시키기 위해 결정화유리가 최근에 새로운 유약 재료로서 소개되고 있다. 신 유약의 연구에 사용된 조성은 $Ca_2$ZrSi$_4$O$_{12}$ 상에 근접하는 CaO-ZrO$_2$-SiO$_2$계의 유리조성의 분말로, 마이크로파 가열 (2.45 GHz)에 의해서 900-120$0^{\circ}C$의 0-20분간 소성되어 평가되었다. 그 결과, 100$0^{\circ}C$ 이상에서 소성한 시편은 내부 결정화를 나타내었으며, 결정상은 미세(5$mu extrm{m}$)한 크기를 갖는 $Ca_2$ZrSi$_4$O$_{12}$가 주 결정상이며, $Ca_2$ZrSi$_4$O$_{12}$, CaSiO$_3$, SiO$_2$의 세 상이 나타났다. 소결체의 미세구조는 사용한 유리분말의 입도의 영향을 받았다. 미세분말 (<38$\mu\textrm{m}$)을 이용한 소결체의 조직이 조세분말 (45-150$\mu\textrm{m}$)의 경우보다 수축율면에서 높았으며 낮은 기공도를 갖는 미세구조를 가졌다. 마이크로파에 의한 유리분말의 소성은 1000-120$0^{\circ}C$ 구간에서 10분 이내 결정화가 완료되는 급속 가열 공정이었으며 CaO-ZrO$_2$-SiO$_2$계 결정화 유리 제조에 균일한 체적가열을 할 수 있었다.

• Journal of the Korean Ceramic Society
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• v.28 no.1
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• pp.53-59
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• 1991

The reaction product between Si3N4 and ZrO2 has been studied by heat treatment of Si3N4-Zr(Y)O2 composite in high vacuum(<10-5 torr) and in air at $700^{\circ}C$. ZrN was formed after heat treatment in vacuum and easily oxidized after heat treatment in air. The amount of ZrN is related to the Y2O3 content dissolved in ZrO2. After the heat treatment in air the toughness increased and the spalling due to the oxidation of ZrN in specimen surface was observed. As a result, it is suggested that the formation of ZrN phase in Si3N4-ZrO2 composite enhance the toughness of the composite in an oxidation conditon.

• Journal of the Korean Ceramic Society
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• v.32 no.5
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• pp.617-625
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• 1995

In order to reduce reflectance of soda-lime glass having average reflectance of 7.35% and refractive index of 1.53, single (SiO2), double (SiO2/20SiO2-80ZrO2), and triple (SiO2/ZrO2/75SiO2-25ZrO2) layers were designed and fabricated on the glass substrate by Sol-Gel method. Stble sols of SiO2-ZrO2 binary system for antireflective (AR) coatings were synthesized with tetraethyl orthosilicate (TEOS) and zirconium n-butoxide as precursors and ethylacetoacetate (EAcAc) as a chelating agent in an atmosphere environment. Films were deposited on soda-lime glass at the withdrawal rates of 3~11 cm/min using the prepared polymeric sols by dip-coating and they were heat-treated at 45$0^{\circ}C$ for 10 min to obtain homogeneous, amorphous and crack-free films. In case of SiO2-ZrO2 binary system, refractive index of film increased with an increase of ZrO2 mol%. Designed optical constant of films could be obtained through varying the withdrawal rate. In the visible region (380~780nm), reflectance was measured with UV/VIS/NIR Spectrophotometer. Average reflectances of the prepared single-layer [SiO2 (n=1.46, t=103nm)], double-layer [SiO2 (n=1.46, t=1-4nm)/20SiO2-80ZrO2 (n=1.81, t=82nm)], and triple-layer [SiO2 (n=1.46, t=104nm)/ZrO2 (n=1.90, t=80nm)/75SiO2-25ZrO2 (n=1.61, t=94 nm)] were 4.74%, 0.75% and 0.38%, respectively.

• Korean Journal of Materials Research
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• v.26 no.2
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• pp.95-99
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• 2016

In this study, 5 um sized $ZrSiO_4$ was ground to 1.9 um, 0.3 um, and 0.1 um sized powders by wet high energy milling process, and the sintering characteristics were observed. Pure $ZrSiO_4$ itself can-not be sintered to these levels of theoretical density, but it was possible to sinter $ZrSiO_4$ powder of nano-scale size of, -0.1 um to the theoretical density and to lower the sintering temperature for full density. Also, the decomposition of $ZrSiO_4$ with a size in the micron range resulted in the formation of monoclinic $ZrO_2$; however, in the nano sized range, the decomposition resulted in the tetragonal phase of $ZrO_2$. So, it was possible to improve the sintering characteristics of nano-sized $ZrSiO_4$ powders.