LTCC용 Glass Frit의 결정화 특성 및 유전 특성에 대한 PbO 함량의 영향

박정현,김용남,송규호,유재영,Park, Jeong-Hyun,Kim, Yong-Nam,Song, Kyu-Ho,Yoo, Jae-Young 한국세라믹학회 2002 한국세라믹학회지 Vol.39 No.5

본 연구에서는 $PbO-TiO_2-SiO_2-BaO-ZnO-Al_2O_3-CaO-B_2O_3-Bi_2O_3-MgO$계의 유리를 $1,400{\circ}C$에서 용융시킨 후, 급랭, 분쇄하여 glass frit을 제조하였다. Glass frit 분말을 일축가압성형한 후 $750~1,000{\circ}C$의 온도범위에서 2시간 동안 소성 및 결정화 하였다. Glass frit의 결정화는 $750{\circ}$ 전후의 온도에서 시작되었고, 저온에서의 주된 결정상은 $Al_2O_3$와 hexagonal celsian($BaAl_2Si_2O_8$)이었다. 소성온도가 높아지면서 monoclinic celsian, $ZnAl_2O_4,\;Zn_2SiO_4,\;CaTi(SiO_4)O,\;TiO_24 등이 주된 결정상으로 나타났고, 특히 celsian은 hexagonal에서 monoclinic으로 상전이가 발생하였다. 그리고 15wt%의 PbO를 첨가한 glass frit에만 $PbTiO_3-CaTiO_3$ 고용체가 나타났다. 1MHz 대역에서 유전특성을 살펴본 결과 유전상수는 11~16이었고, 유전손실은 0.020 미만이었다. 그러나 15wt%의 PbO를 첨가한 glass frit의 경우는 $PbTiO_3-CaTiO_3$ 고용체 결정상의 존재로 유전상수가 17~26으로 높았고, 유전손실은 0.010~0.015로서 다른 조성들에 비하여 우수한 특성을 나타내었다. In this study, the glass frit of $PbO-TiO-2-SiO_2-BaO-ZnO-Al_2O-3-CaO-B_2O_3-Bi_2O_3-MgO$ system was manufactured. The glass was melted at $1,400{\circ}C$, quenched and attrition-milled. The glass frit powder was pressed and fired for 2h at the range of $750~1,000{\circ}C$. The crystallization of glass frit began at about $750{\circ}$ and at low temperature, the main crystal phases were hexagonal celsian($BaAl_2Si_2O_8$) and alumina. As the firing temperature increased, the crystal phases of monoclinic celsian, zinc aluminate, zinc silicate, calcium titanium silicate and titania appeared. And the increase of firing temperature led to transformation of hexagonal celsian to monoclinic. The only glass frit containing 15wt% PbO had the crystal phase of solid solution of $PbTiO_3-CaTiO_3$. At the frequency of 1 MHz, the dielectric constant of glass frit crystallized was in the range of 11~16 and the dielectric loss less than 0.020. But the glass frit containing 15wt% PbO had the dielectric constant of 17~26 and loss of 0.010~0.015 because of crystal phase of solid solution of $PbTiO_3-CaTiO_3$.

두 종류의 다공성 유리막을 이용한 전기삼투 펌프의 비교 연구

권길성(Kilsung Kwon),박철우(Chul-Woo Park),김대중(Daejoong Kim) 대한기계학회 2011 大韓機械學會論文集B Vol.35 No.4

본 연구에서는 두 종류의 다공성 유리막을 이용하여 전기삼투 펌프를 제작하였다. 전기삼투 펌프의 성능은 탈이온수와 1 mM 나트륨 테트라붕산염 데카수화물 완충액을 이용하여 최대유량, 최대전류 그리고 최대압력의 항으로 표현하였다. 최대유량과 최대전류는 ROBU 사의 다공성 유리막의 높은 공극률에 기인하여 DURAN 사의 다공성 유리막 보다 높은 값을 가졌다. 그러나 최대압력은 비슷하였다. 열역학적 효율은 ROBU 사의 다공성 유리막이 DURAN 사의 다공성 유리막보다 2 배 정도 높은 값을 가졌으며, 최대유량당 최대전류 역시 ROBU 사의 다공성 유리막이 높은 값을 가졌다. 그러나 최대압력당 최대전류는 DURAN 사의 다공성 유리막에서 더 높은 값을 가졌다. 본 연구에서는 ROBU 사의 다공성 유리막은 낮은 출력으로 높은 유량을 구현할 수 있고, DURAN 사의 다공성 유리막은 낮은 출력으로 높은 압력을 구현할 수 있음을 확인하였다. Electro-osmotic pumps were fabricated by using two types of porous glass frits. The performance of these pumps was characterized in terms of maximum flow rate, current, and pressure using deionized water and 1 mM sodium tertraborate decahydrate buffer. Maximum flow rate and current when ROBU porous glass frits were used were higher than those when DURAN porous glass frits were used because of the high porosity of the ROBU glass frits. However, the maximum pressure when ROBU glass frits were used was similar to that when DURAN glass frits were used. The therrmodynamic efficiency of a pump with ROBU porous glass frits is approximately twice that of a pump with DURAN porous glass frits. Further, the maximum flow rate at maximum current in the case of ROBU porous glass frits is high. However, it is lower than the maximum pressure at maximum current in the case of DURAN porous glass frits. Further, in this study, we also verified the effectiveness of ROBU glass frits when high flow rate is required and of DURAN glass frits when a high pressure is required.

Glass Frit의 입도가 MLCC 외부전극 Paste의 소결거동에 미치는 영향

이규하,전병준,김창훈,권영근,박명준,구현희,엄지원,김영태,허강헌 한국세라믹학회 2009 한국세라믹학회지 Vol.46 No.2

Multilayer ceramic capacitors (MLCCs) have continually been made smaller in size and larger in capacity in resent years. However, the end termination electrode is still thick in many MLCCs. In this study, we used small grain glass frit to embody thin film and highly densification in the end termination by improve sintering driving force with well-dispersion and rising surface energy. Pastes were fabricated using size changed glass frit, such as 0.1 µm, 0.5 µm, 1.0 µm, 4.0 µm. Fabricated pastes were applied 05A475KQ5 chip and fired various sintering temperatures to analyze sintering behavior of pastes. Consequently, small glass frit used pastes have many merits than larger, such as well-dispersion, improve cornercoverage and surface roughness, possibility of low temperature sintering. However, we confirmed that small glass frit used pastes have narrow sintering window by rapid completion of sintering densification. Multilayer ceramic capacitors (MLCCs) have continually been made smaller in size and larger in capacity in resent years. However, the end termination electrode is still thick in many MLCCs. In this study, we used small grain glass frit to embody thin film and highly densification in the end termination by improve sintering driving force with well-dispersion and rising surface energy. Pastes were fabricated using size changed glass frit, such as 0.1 µm, 0.5 µm, 1.0 µm, 4.0 µm. Fabricated pastes were applied 05A475KQ5 chip and fired various sintering temperatures to analyze sintering behavior of pastes. Consequently, small glass frit used pastes have many merits than larger, such as well-dispersion, improve cornercoverage and surface roughness, possibility of low temperature sintering. However, we confirmed that small glass frit used pastes have narrow sintering window by rapid completion of sintering densification.

Additional Study on the Laser Sealing of Dye-Sensitized Solar-Cell-Panels Using V₂O₅ and TeO₂ Containing Glass

Cho, Sung-Jin,Lee, Kyoungho The Korean Ceramic Society 2015 한국세라믹학회지 Vol.52 No.2

The effective glass frit composition used to absorb laser energy and to seal commercial dye-sensitized solar cell panel substrates has been previously developed using $V_2O_5-TeO_2$-based glass with 10 wt% ${\beta}$-eucryptite as a CTE controlling filler. The optimum sealing conditions are provided using a 3 mm beam, a laser power of 40 watt, a scan speed of 300 mm/s, and 200 irradiation cycles. In this study, the feasibility of the developed glass frit is investigated in terms of the sealing strength and chemical durability against the commercial iodide/triiodide electrolyte solution and fluorine-doped tin oxide (FTO) electrode in order to increase the solar cell lifetime. The sealing strength of the laser-sealed $V_2O_5-TeO_2$-based glass frit is $20.5{\pm}1.7MPa$, which is higher than those of thermally sealed glass frit and other reported glass frit. Furthermore, the developed glass frit is chemically stable against electrolyte solutions. The glass frit constituents are not leached out from the glass after soaking in the electrolyte solution for up to three months. During the laser sealing, the glass frit does not react with the FTO electrode; thus, the resistivity of the FTO electrode beneath the laser-sealed area remains the same.

Additional Study on the Laser Sealing of Dye-Sensitized Solar-Cell-Panels Using V2O5 and TeO2 Containing Glass

조성진,이경호 한국세라믹학회 2015 한국세라믹학회지 Vol.52 No.2

The effective glass frit composition used to absorb laser energy and to seal commercial dye-sensitized solar cell panel substrates has been previously developed using V2O5-TeO2-based glass with 10 wt% β-eucryptite as a CTE controlling filler. The optimum sealing conditions are provided using a 3 mm beam, a laser power of 40 watt, a scan speed of 300 mm/s, and 200 irradiation cycles. In this study, the feasibility of the developed glass frit is investigated in terms of the sealing strength and chemical durability against the commercial iodide/triiodide electrolyte solution and fluorine-doped tin oxide (FTO) electrode in order to increase the solar cell lifetime. The sealing strength of the laser-sealed V2O5-TeO2-based glass frit is 20.5 ± 1.7 MPa, which is higher than those of thermally sealed glass frit and other reported glass frit. Furthermore, the developed glass frit is chemically stable against electrolyte solutions. The glass frit constituents are not leached out from the glass after soaking in the electrolyte solution for up to three months. During the laser sealing, the glass frit does not react with the FTO electrode; thus, the resistivity of the FTO electrode beneath the laser-sealed area remains the same.

Role of PbO-Based Glass Frit in Ag Thick-Film Contact Formation for Crystalline Si Solar Cells

홍경국,조성빈,Ji-Weon Jeong,허주열,Hyun Jung Park 대한금속·재료학회 2009 METALS AND MATERIALS International Vol.15 No.2

The reactions between Ag pastes containing two types of PbO-based glass frits and an n-type (100) Si wafer during firing in air at 800 °C were investigated in order to understand the mechanism for the formation of inverted pyramidal Ag crystallites at the Si interface as well as the effect of the PbO content of the glass frit on Ag crystallite formation. Inverted pyramidal Ag crystallites were formed by the precipitation of Ag atoms dissolved in fluidized glass during the subsequent cooling process after firing. PbO in the glass frit did not participate directly in the reaction with the Si wafer. However, its content had a strong influence on the reaction rate at the glass/Si interface and, thus, on the size and distribution of the Ag crystallites. The effect of the PbO content in the glass could be understood from the higher Ag solubility and lower viscosity of the glass at the firing temperature with increasing PbO content. Based on the experimental results, a model was proposed for the formation of Ag crystallites at the glass/Si interface during the firing process of screen-printed thick-film Ag metallization. The reactions between Ag pastes containing two types of PbO-based glass frits and an n-type (100) Si wafer during firing in air at 800 °C were investigated in order to understand the mechanism for the formation of inverted pyramidal Ag crystallites at the Si interface as well as the effect of the PbO content of the glass frit on Ag crystallite formation. Inverted pyramidal Ag crystallites were formed by the precipitation of Ag atoms dissolved in fluidized glass during the subsequent cooling process after firing. PbO in the glass frit did not participate directly in the reaction with the Si wafer. However, its content had a strong influence on the reaction rate at the glass/Si interface and, thus, on the size and distribution of the Ag crystallites. The effect of the PbO content in the glass could be understood from the higher Ag solubility and lower viscosity of the glass at the firing temperature with increasing PbO content. Based on the experimental results, a model was proposed for the formation of Ag crystallites at the glass/Si interface during the firing process of screen-printed thick-film Ag metallization.

복합기법을 적용한 현대 스테인드글라스의 범위 확장 가능성에 대한 연구

배진희,정수경 사단법인 한국조형디자인협회 2022 조형디자인연구 Vol.25 No.1

This paper is a study on the expandability of the scope and concept of modern stained glass with composite techniques. The possibility of pictorial expression of light was examined through stained glass with a glass fusing technique centered on a glass fusing technique using Frit. In addition, based on a study on the possibility of pictorial expression of stained glass, it was confirmed that the scope of its application was further expanded from church architecture and can be applied in various ways to general architecture. The introduction of this study examined the change in the concept of modern stained glass by presenting a new trend of modern stained glass in Europe before and after World War II. In addition, this researcher's work tendency was greatly influenced, and examples of works by European artists Udo Zembok (1951-) and Thierry Boissel (1962-), who applied a composite technique centered on glass fusing technique using frit to architecture were studied. In addition, the trend continued to study the trend of domestic stained glass in a new phase and looked at the composites technique stained glass that emphasized the trend of this researcher's painting work. Finally, it was intended to present the possibility of implementing 'light painting' through stained glass to which a composite technique based on pictorial expression is applied and introducing it as part of architectural art. We hope that further follow-up studies will be conducted based on this study, and we hope that Korea's modern stained glass can develop more diversely. 본 논문은 복합기법을 도입한 현대 스테인드글라스의 범위와 개념의 확장 가능성에 관한 연구이다. 프리트(Frit)를 활용한 글라스 퓨징(Glass Fusing)기법 중심의 복합기법이 적용된 스테인드글라스를 통해 빛의 회화적 표현의 가능성을 고찰했다. 또한 스테인드글라스의 회화적 표현 가능성에 관한 연구를 바탕으로 그 적용 범위를 교회건축에서 더욱 확장해 일반건축에까지 다양하게 적용할 수 있음을 확인했다. 본 연구의 도입부에서는 제2차 세계대전 전후의 유럽 현대 스테인드글라스의 새로운 흐름을 제시하며 현대 스테인드글라스의 개념 변화를 고찰했다. 그리고 본 연구자의 작품 성향에 지대한 영향을 주었으며, 프리트를 이용한 글라스 퓨징기법 중심의 복합기법을 회화적으로 건축에 적용한 유럽의 작가 우도 젬복(Udo Zembok, 1951-)과 티에리 부아셀(Thierry Boissel, 1962-)의 작품 사례를 연구했다. 또한 그 흐름이 이어져 새로운 국면을 맞은 국내 스테인드글라스 경향을 연구하고, 회화적 경향이 강조된 본 연구자의 복합기법 스테인드글라스를 살펴보았다. 마지막으로 회화적 표현을 기반으로 한 복합기법이 적용된 스테인드글라스를 통해 ‘빛의 회화’를 구현하고 건축적 예술로 도입할 수 있는 가능성을 제시하고자 했다. 본 연구를 토대로 향후 심화된 후속 연구가 이어지기를 바라며, 한국 현대 스테인드글라스의 다채로운 발전을 기대해본다.

PDP용 Ag전극 페이스트의 Bi계 프릿 제조 및 특성

김형수,최정철,이병옥,최승철 한국마이크로전자및패키징학회 2003 마이크로전자 및 패키징학회지 Vol.10 No.4

PDP전극용 Ag전극 페이스트의 프릿으로 기존의 Pb-based 프릿을 대신 할 수 있는 Bi-based 조성의 새로운 유리조성의 가능성을 검토하였다. PDP디스플레이 응용을 위해 프릿의 저융점화 및 열팽창계수 제어를 행하였고, 이를 전극 페이스트 제조에 적용하여 스크린 프린팅된 전극을 평가하였다. $Bi_2O_3$를 50-60wt%이상 첨가된 $Bi_2O_3-B_2O_3-Al_2O_3$계 조성의 프릿은 연화점이 400∼$480^{\circ}C$, 열팽창계수가 7.31∼$10.02\times 10^{-6}/^{\circ}C$이며, 전극의 단자저항은 4.1∼4.8$\Omega$ 이었다. 본 연구에서 새로이 개발된 Bi계 프릿조성은 Pb계 조성의 프릿에 상당하는 물성을 얻을 수 있었으며, 이를 전극용 페이스트에 적용한 결과, 전극 프린팅에서 퍼짐성과 균일성이 우수하였다. PDP전극용 무연, 무 알카리 프릿으로 Bi계 조성의 적용가능성을 확인할 수 있었다. A new type of Bi based glass frit was developed for Ag paste in PDP applications and its properties are compared with the commercially used Pb based glass frit. After optimization of the properties of Bi based frits for PDP application such as the softening temperature and the coefficient of thermal expansion (C.T.E), the screen printed electrodes prepared with the Bi based fit contained Ag paste were characterized. In $Bi_2O_3-B_2O_3-Al_2O_3$ glass system with the more than 50% of $Bi_2O_3$, the softening temperature, the thermal expansion coefficient and the line resistivity was 400∼$480^{\circ}C$, 7.31∼$10.02\times 10^{-6}/^{\circ}C$> and 4.1∼4.8$\Omega$ respectively. Properties of the Bi based frits are comparable with the Pb based frits. A printability and an uniformity of the Bi based frits were excellent in screen printed Ag eletrode. The Bi based frit system is an excellent candidate material for Pb free and Alkali free frit in PDP applications.

Glass 첨가량에 따른 ZnO 바리스터의 전기적 특성

조현무,이종덕,박상만,이성갑,Cho, Hyun-Moo,Lee, Jong-Deok,Park, Sang-Man,Lee, Sung-Gap 한국전기전자재료학회 2005 전기전자재료학회논문지 Vol.18 No.9

ZnO varistor ceramics were fabricated with variation of addition of glass-frit amount and the sintering temperature was $1100^{\circ}C$. The average grain sizes were showed increased from $8.6{\mu}m\;to\;10{\mu}m$, and varistor voltages were decreased from 506V to 460V by added amount of glass-frit. Nonlinear coefficient $\alpha$, of all were with increasing the amount of glass-frit more than 70, in case of added on $0.03wt\%$ glass-frit was 83. And leakage current were less than $1{\mu}A$ with applied at $82\%$ of varistor voltage. The clamping voltage ratio of the specimens added $0.03wt\%$ glass-frit was 1.41 at applied 25A $[8/20\;{\mu}s]$. In the specimen added $0.03wt\%$ glass-frit, endurance of surge current and deviation of varistor voltage were $6200A/cm^2,\;\Delta-1.67\%$, respectively and clamping voltage ratio was 2.33. In the Specimen added $0.03wt\%$ glass-frit were superior to any other compositions on High Temperature Load Test(HTLT) for 1000 hr at $85^{\circ}C$, and deviation of the varistor voltage were $\Delta-1.29\%$.

알루미늄 Paste의 Glass frit 첨가에 따른 Al-Si alloy 층의 변화

송주용(Song, Jooyong),박성은(Park, Sungeun),김성탁(Kim, Seongtak),김현호(Kim, Hyunho),강민구(Kang, Min Gu),탁성주(Tark, Sung Ju),이병철(Lee, Byungchul),김동환(Kim, Donghwan) 한국신재생에너지학회 2010 한국신재생에너지학회 학술대회논문집 Vol.2010 No.06

스크린 프린팅을 이용한 태양전지에서 전극소성 시 알루미늄 후면 전극이 실리콘으로 확산되어 후면전계(Back Surface Field)를 형성한다. 후면전계 형성시 알루미늄과 후면전계 사이에 알루미늄-실리콘 합금이 형성된다. 이 알루미늄-실리콘 합금은 알루미늄 후면전극의 전기전도도 및 휨현상, bead 형성 등에 영향을 끼친다. 본 논문은 알루미늄 페이스트에 첨가된 Glass frit이 알루미늄-실리콘 합금 형성에 끼치는 영향을 관찰하였다. 분산제, 유기바인더, 알루미늄을 섞어 1개의 페이스트를 만들었고, Glass frit을 1%, 2%, 3%, 4%, 5% 씩 첨가하여 총 6개의 알루미늄 페이스트를 만들었다. 절삭손상이 제거된 실리콘 기판의 후면에 알루미늄 페이스트를 스크린 프린팅하여 전극을 소성하였다. 주사전자 현미경(SEM)을 사용하여 시편의 단면사진으로부터 Glass frit 함량에 따른 알루미늄-실리콘 합금층의 변화를 관찰하였다. Glass frit이 첨가되지 않은 페이스트는 소성 후 알루미늄-실리콘 합금이 두껍게 형성되었으나, Glass frit이 첨가된 페이스트는 소성 후 알루미늄-실리콘 합금이 얇게 형성되는 결과를 얻었다. 또한 Glass frit을 첨가함에 따라 표면의 원형 모양의 무늬가 작아지면서 3%부터는 사라지는 것을 확인할 수 있었다.