Dinickel-silicide (Ni2Si)/glass was employed as a counter electrode for a dye-sensitized solar cell (DSSC) device. Ni2Si was formed by rapid thermal annealing (RTA) at 700 oC for 15 seconds of a 50 nm-Ni/50 nm-Si/glass structure. For comparison, Ni2Si on quartz was also prepared through conventional electric furnace annealing (CEA) at 800 oC for 30 minutes. XRD, XPS, and EDS line scanning of TEM were used to confirm the formation of Ni2Si. TEM and CV were employed to confirm the microstructure and catalytic activity. Photovoltaic properties were examined using a solar simulator and potentiostat. XRD, XPS, and EDS line scanning results showed that both CEA and RTA successfully led to tne formation of nano thick- Ni2Si phase. The catalytic activity of CEA-Ni2Si and RTA-Ni2Si with respect to Pt were 68 % and 56 %. Energy conversion efficiencies (ECEs) of DSSCs with CEA-Ni2Si and RTA-Ni2Si catalysts were 3.66 % and 3.16 %, respectively. Our results imply that nano-thick Ni2Si may be used to replace Pt as a reduction catalytic layer for a DSSCs. Moreover, we show that nanothick Ni2Si can be made available on a low-cost glass substrate via the RTA process.

The cobalt silicides were investigated for employment as a catalytic layer for a DSSC. Using an E-gun evaporation process, we prepared a sample of 100 nm-thick cobalt on a p-type Si (100) wafer. To form cobalt silicides, the samples were annealed at temperatures of 300 oC, 500 oC, and 700 oC for 30 minutes in a vacuum. Four-point probe, XRD, FE-SEM, and CV analyses were used to determine the sheet resistance, phase, microstructure, and catalytic activity of the cobalt silicides. To confirm the corrosion stability, we also checked the microstructure change of the cobalt silicides after dipping into iodide electrolyte. Through the sheet resistance and XRD results, we determined that Co2Si, CoSi, and CoSi2 were formed successfully by annealing at 300 oC, 500 oC, and 700 oC, respectively. The microstructure analysis results showed that all the cobalt silicides were formed uniformly, and CoSi and CoSi2 layers were very stable even after dipping in the iodide electrolyte. The CV result showed that CoSi and CoSi2 exhibit catalytic activities 67 % and 54 % that of Pt. Our results for Co2Si, CoSi, and CoSi2 revealed that CoSi and CoSi2 could be employed as catalyst for a DSSC.

We fabricated thermally evaporated 30 nm-Ni/(20 nm or 60 nm)a-Si:H/Si films to investigate the energy-saving property of silicides formed by rapid thermal annealing (RTA) at temperatures of 350˚C, 450˚C, 550˚C, and 600˚C for 40 seconds. A transmission electron microscope (TEM) and a high resolution X-ray diffractometer (HRXRD) were used to determine the cross-sectional microstructure and phase changes. A UVVIS-NIR and FT-IR (Fourier transform infrared spectroscopy) were employed for near-IR and middle-IR absorbance. Through TEM and HRXRD analysis, for the nickel silicide formed at low temperatures below 450˚C, we confirmed columnar-shaped structures with thicknesses of 20~30 nm that had δ-Ni2Si phases. Regarding the nickel silicide formed at high temperatures above 550˚C, we confirmed that the nickel silicide had more than 50 nm-thick columnar-shaped structures with a Ni31Si12 phase. Through UV-VIS-NIR analysis, nickel silicide showed almost the same absorbance in the near IR region as well as ITO. However, in the middle IR region, the nickel silicides with low temperature showed similar absorbance to those from high temperature silicidation.

Thermally evaporated 10 nm-Ni/1 nm-Au/(30 nm-poly)Si structures were fabricated in order to investigate the thermal stability of Au-inserted nickel silicide. The silicide samples underwent rapid thermal annealing at 300~1100˚C for 40 seconds. The sheet resistance was measured using a four-point probe. A scanning electron microscope and a transmission electron microscope were used to determine the cross-sectional structure and surface image. High-resolution X-ray diffraction and a scanning probe microscope were employed for the phase and surface roughness. According to sheet resistance and XRD analyses, nickel silicide with Au had no effect on widening the NiSi stabilization temperature region. Au-inserted nickel silicide on a single crystal silicon substrate showed nano-dots due to the preferred growth and a self-arranged agglomerate nano phase due to agglomeration. It was possible to tune the characteristic size of the agglomerate phase with silicidation temperatures. The nano-thick Au-insertion was shown to lead to self-arranged microstructures of nickel silicide.

Nanostructured and composite powders have been prepared by mechanochemical reaction from mixtures of Ti, BN, and powders. The raw materials have reacted to form a uniform mixture of TiN, and or depending on the amount of used in the starting mixtures, and the reaction proceeded through so-called mechanically activated self-sustaining reaction (MSR). Fine TiN and crystallites less than a few tens of nanometer were homogeneously dispersed in the amorphous or matrix after milling for 12 hours. These amorphous matrices became crystalline phases after annealing at high temperatures as expected, but the original microstructure did not change significantly

실리사이드반웅을 이용하여 니켈모노실리사이드의 양측계면에 단결정실리콘을 적층시켜 전도성이 우수하며 식각특성이 달라 MEMS용 기판으로 채용이 가능한 SOS (Silicon-on-Silicide) 기판을 제작하였다. 실리콘 기판 전면에 Ni를 열증착법으로 1000Å두께로 성막하고, 실리콘 기판 경면과 맞블여 후 300~900˚C온도범위에서 15시간동안 실리사이드 처리하여 니켈모노실리사이드가 접합매체로 되는 기판쌍들을 완성하였다. 완성된 기판쌍들은 IR (infrared) 카메라를 이용하여 비파괴적으로 접합상태를 확인하고. 주사전자현미경 (scaning electron microscope)과 투과전자현미경 (tranmission electron microscope)을 이용하여 수직단면 미세구조를 확인하였다. Ni 실리사이드의 상변화가 일어나는 온도를 제외하고는 Si NiSi ∥Si 기판쌍은 기판전면에 52%이상 완전접합이 진행되었음을 확인하였고 생성 실리사이드의 두께에 따라 나타나는 명암부에 비추어 기판쌍 중앙부에 두꺼운 니켈노실리아드가 형성되었다고 판단되었다. 완성된 Si NiSi ∥ Si 기판쌍을 SBM 수직단면에 의괘 확인한 결과 접합이 완성된 기판중심부의 접합계면은 1000Å 두께의 NiSi가 균일하게 형성되었으며 배율 30,000배의 해상도에서 계면간 분리부분없이 완전한 접합이 진행되었음을 확인하였다. 반면 기판쌍 에지 (edge)부분에는 실리사이드가 헝성되지 않은 비접합상태가 발견되었다. 수직단면루과전자현미경 결과물에 근거하여 접합된 중심부에서는 피접합되는 실리콘의 경면과 니켈이 성막된 실리콘 경면 상부계면에 10-20Å의 비정질막이 발견되었으며, 산화막으로 추정되는 이 막이 접합률을 현저히 저하시키는 것을 확인하였다. 접합이 진행되지 않은 에지부는 이러한 산화막이 열처리 진행중 급격히 성장하여 피접합 실리콘층의 분리가 발생하였다. 따라서 Si NiSi ∥Si 기판쌍의 접합률을 향상시키기 위해서는 피접합 실리콘 계면과 Ni 상부층간의 비정질부를 적극적으로 제거하여야 함을 알 수 있었다.

Ni mono-silicide는 선폭이 0.15μm이하에서도 전기저항이 커지는 현상이 없고 Ni와 Si이 1:1로 반응하기 때문에 얇은 실리사이드의 제조가 가능하고 도펀트의 재분포 현상을 감소시킬수 있다. 따라서 0.15μm급 이하 디바이스에 사용이 기대되는 NiSi의 제조를 위한 Ni 박막의 증착조건 확보와 열처리 조건에 따른 NiSi의 기초 물성조사를 수행하였다. Ni mono-silicide는 sputter의 물리적 증착방법으로 Ni 박박을 증착후 관상로를 상용하여 150~1000˚C 온도 범위에서 제조하였다. 그후 SPM을 이용하여 각 시편의 표면조도를 측정하였고, 미세구조와 성분분석은 EDS가 장착된 TEM을 사용하여 측정하였다. 각 열처리 온도별 생성상의 전기적 성질은 4 point probe로 측정하였다. 본 연구의 결과, SPM은 비파괴 방법으로 NiSi가 NiSi2로 변태되었는지 확인할 수 있는 효과적인 공정모니터링 방법임을 확인하였고, 800˚C이상 공온 열처리에 잔류 Ni의 산화방지를 의해 산소분압의 제어가 Po2=1.5±10(sup)-11색 이하가 되어야 함을 알 수 있었으며, 전지적 특성실험으로부터 본 연구에서 제조된 박막의 NiSi→NiSi2 상태변온도는 700˚C라고 판단되었다.

The synthesis of and NiSi has been investigated by mechanical alloying (MA) of Ni-27.9at%Si, Ni-33.3at%Si and Ni-50.0at%Si powder mixtures. As-received and premilled elemental powders were subjected to MA. The as-received Ni powder was spherical and the mean particle size 48.8m, whereas the premilled Ni powder was flaky and the mean particle diameter and thickness were found to be 125 and 5m, respectively. The mean surface area of the premilled Mi powder particle was 3.5 times as large as that of the as-received Ni powder particle. The as-received Si powder was was 10.0m. Self-propagating high-temperature synthesis (SHS) reaction, followed by a slow reaction (a solid state diffusion), was observed to produce each Ni silicide during MA of the as-received elemental powders. In other word , the reactants and product coexisted for a long period of MA of time. Only SHS reaction was, however, observed to produce each Ni silicide during MA of the premilled elemental powders, indicating that each Ni sillicide formed rather abruptly at a short period of MA time. The mechanisms and reaction rates for the formation of the Ni silicides appeared to be influenced by the elemental powder particle size and shape as well as the heat of formation of the products longrightarrow-43.1kJ/mol.at., -47.6kJ/mol.at.).

Nickel silicides (Si, NiSi and NiSi) have been synthesized by mechanical alloying (MA) of Ni-27.9at.9at%Si, Ni-33.3at% and Ni-50.0at% powder mixtures, respectively. From in situ thermal analysis, eash citical milling period for the formation of the three phases was observed to be 40.2, 34.9 and 57.5 min, at which there was a rapid increase in temperature. This indicates that rapid, self-propagating high-temperature synthesis (SHS) reactions were observed to produce the three phases during room-temperature high-energy ball milling of elemental powders. Each Ni silicide, Ni and Si, however, coexisted for an extended milling time even after the critical milling period. The powders mechanically alloyed after the critical period showed the rapid increase in microhardness. The Hv values were found to be higher than 1000kgf/mm. The formation of nickel silicides by mechanical alloying and the relevant reaction rates appeared to be influenced by the critical milling period and the heat of formation of the products involved (Si-43.1kJ/mol.at., NiSi-47.6kJ/mol.at., NiSi-42.4kJ/mol.at).

The synthesis of titanium silicides (, , , and TiSi) by mechanical alloying has been investigated. Rapid, self-propagating high-temperature synthesis (SHS) reactions were observed to produce the last three phases during room-temperature high-energy ball milling of elemental powders. Such reactions appeared to be ignited by mechanical impact in an intimate, fine powder mixture formed after a critical milling period. During the high-energy ball milling, the repeated impact at contact points leads to a local concentration of energy which may ignite a self-propagating reaction. From in-situ thermal analysis, each critical milling period for the formation of , and TiSi was observed to be 22, 35.5 and 53.5 min, respectively. and , however, have not been produced even till the milling period of 360 min due to lack of the homogeneity of the powder mixtures. The formation of titanium silicides by mechanical alloying and the relevant reaction rates appeared to depend upon the critical milling period, the homogeneity of the powder mixtures, and the heat of formation of the products involved.

Co 단일층과 Co/Ti 이중층으로부터 형성된 코발트 실리사이드를 최종 막의 구조와 에피텍셜 성장 측면에서 조사하였다. Co 단일층은 그 두께와는 관계없이 전체 막이 CoSi2로 변화된 반면에, Co/Ti 이중층 구조에서는 Co와 Ti 막의 두께비가 최종막 구조에 상당한 영향을 주었다. 그리고 CoSi2막의 에피 성장이 Co 단일층에서 보다는 Co/Ti 이중층에서 보다 용이하였다.