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CMOS 소자 응용을 위한 Plasma doping과 Silicide 형성

  • Choe, Jang-Hun;Do, Seung-U;Seo, Yeong-Ho;Lee, Yong-Hyeon
    • Proceedings of the Korean Vacuum Society Conference
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    • 2010.02a
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    • pp.456-456
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    • 2010
  • CMOS 소자가 서브마이크론($0.1\;{\mu}m$) 이하로 스케일다운 되면서 단채널 효과(short channel effect), 게이트 산화막(gate oxide)의 누설전류(leakage current)의 증가와 높은 직렬저항(series resistance) 등의 문제가 발생한다. CMOS 소자의 구동전류(drive current)를 높이고, 단채널 효과를 줄이기 위한 가장 효율적인 방법은 소스 및 드레인의 얕은 접합(shallow junction) 형성과 직렬 저항을 줄이는 것이다. 플라즈마 도핑 방법은 플라즈마 밀도 컨트롤, 주입 바이어스 전압 조절 등을 통해 저 에너지 이온주입법보다 기판 손상 및 표면 결함의 생성을 억제하면서 고농도로 얕은 접합을 형성할 수 있다. 그리고 얕은 접합을 형성하기 위해 주입된 불순물의 활성화와 확산을 위해 후속 열처리 공정은 높은 온도에서 짧은 시간 열처리하여 불순물 물질의 활성화를 높여주면서 열처리로 인한 접합 깊이를 얕게 해야 한다. 그러나 접합의 깊이가 줄어듦에 따라서 소스 및 드레인의 표면 저항(sheet resistance)과 접촉저항(contact resistance)이 급격하게 증가하는 문제점이 있다. 이러한 표면저항과 접촉저항을 줄이기 위한 방안으로 실리사이드 박막(silicide thin film)을 형성하는 방법이 사용되고 있다. 본 논문에서는 (100) p-type 웨이퍼 He(90 %) 가스로 희석된 $PH_3$(10 %) 가스를 사용하여 플라즈마 도핑을 실시하였다. 10 mTorr의 압력에서 200 W RF 파워를 인가하여 플라즈마를 생성하였고 도핑은 바이어스 전압 -1 kV에서 60 초 동안 실시하였다. 얕은 접합을 형성하기 위한 불순물의 활성화는 ArF(193 nm) excimer laser를 통해 $460\;mJ/cm^2$의 에니지로 열처리를 실시하였다. 그리고 낮은 접촉비저항과 표면저항을 얻기 위해 metal sputter를 통해 TiN/Ti를 $800/400\;{\AA}$ 증착하고 metal RTP를 사용하여 실리사이드 형성 온도를 $650{\sim}800^{\circ}C$까지 60 초 동안 열처리를 실시하여 $TiSi_2$ 박막을 형성하였다. 그리고 $TiSi_2$의 두께를 측정하기 위해 TEM(Transmission Electron Microscopy)을 측정하였다. 화학적 결합상태를 분석하기 위해 XPS(X-ray photoelectronic)와 XRD(X-ray diffraction)를 측정하였다. 접촉비저항, 접촉저항과 표면저항을 분석하기 위해 TLM(Transfer Length Method) 패턴을 제작하여 I-V 특성을 측정하였다. TEM 측정결과 $TiSi_2$의 두께는 약 $580{\AA}$ 정도이고 morphology는 안정적이고 실리사이드 집괴 현상은 발견되지 않았다. XPS와 XRD 분석결과 실리사이드 형성 온도가 $700^{\circ}C$에서 C54 형태의 $TiSi_2$ 박막이 형성되었고 가장 낮은 접촉비저항과 접촉저항 값을 가진다.

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Sesquiterpenoids Bioconversion Analysis by Wood Rot Fungi

  • Lee, Su-Yeon;Ryu, Sun-Hwa;Choi, In-Gyu;Kim, Myungkil
    • 한국균학회소식:학술대회논문집
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    • 2016.05a
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    • pp.19-20
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    • 2016
  • Sesquiterpenoids are defined as $C_{15}$ compounds derived from farnesyl pyrophosphate (FPP), and their complex structures are found in the tissue of many diverse plants (Degenhardt et al. 2009). FPP's long chain length and additional double bond enables its conversion to a huge range of mono-, di-, and tri-cyclic structures. A number of cyclic sesquiterpenes with alcohol, aldehyde, and ketone derivatives have key biological and medicinal properties (Fraga 1999). Fungi, such as the wood-rotting Polyporus brumalis, are excellent sources of pharmaceutically interesting natural products such as sesquiterpenoids. In this study, we investigated the biosynthesis of P. brumalis sesquiterpenoids on modified medium. Fungal suspensions of 11 white rot species were inoculated in modified medium containing $C_6H_{12}O_6$, $C_4H_{12}N_2O_6$, $KH_2PO_4$, $MgSO_4$, and $CaCl_2$ for 20 days. Cultivation was stopped by solvent extraction via separation of the mycelium. The metabolites were identified as follows: propionic acid (1), mevalonic acid lactone (2), ${\beta}$-eudesmane (3), and ${\beta}$-eudesmol (4), respectively (Figure 1). The main peaks of ${\beta}$-eudesmane and ${\beta}$-eudesmol, which were indicative of sesquiterpene structures, were consistently detected for 5, 7, 12, and 15 days These results demonstrated the existence of terpene metabolism in the mycelium of P. brumalis. Polyporus spp. are known to generate flavor components such as methyl 2,4-dihydroxy-3,6-dimethyl benzoate; 2-hydroxy-4-methoxy-6-methyl benzoic acid; 3-hydroxy-5-methyl phenol; and 3-methoxy-2,5-dimethyl phenol in submerged cultures (Hoffmann and Esser 1978). Drimanes of sesquiterpenes were reported as metabolites from P. arcularius and shown to exhibit antimicrobial activity against Gram-positive bacteria such as Staphylococcus aureus (Fleck et al. 1996). The main metabolites of P. brumalis, ${\beta}$-Eudesmol and ${\beta}$-eudesmane, were categorized as eudesmane-type sesquiterpene structures. The eudesmane skeleton could be biosynthesized from FPP-derived IPP, and approximately 1,000 structures have been identified in plants as essential oils. The biosynthesis of eudesmol from P. brumalis may thus be an important tool for the production of useful natural compounds as presumed from its identified potent bioactivity in plants. Essential oils comprising eudesmane-type sesquiterpenoids have been previously and extensively researched (Wu et al. 2006). ${\beta}$-Eudesmol is a well-known and important eudesmane alcohol with an anticholinergic effect in the vascular endothelium (Tsuneki et al. 2005). Additionally, recent studies demonstrated that ${\beta}$-eudesmol acts as a channel blocker for nicotinic acetylcholine receptors at the neuromuscular junction, and it can inhibit angiogenesis in vitro and in vivo by blocking the mitogen-activated protein kinase (MAPK) signaling pathway (Seo et al. 2011). Variation of nutrients was conducted to determine an optimum condition for the biosynthesis of sesquiterpenes by P. brumalis. Genes encoding terpene synthases, which are crucial to the terpene synthesis pathway, generally respond to environmental factors such as pH, temperature, and available nutrients (Hoffmeister and Keller 2007, Yu and Keller 2005). Calvo et al. described the effect of major nutrients, carbon and nitrogen, on the synthesis of secondary metabolites (Calvo et al. 2002). P. brumalis did not prefer to synthesize sesquiterpenes under all growth conditions. Results of differences in metabolites observed in P. brumalis grown in PDB and modified medium highlighted the potential effect inorganic sources such as $C_4H_{12}N_2O_6$, $KH_2PO_4$, $MgSO_4$, and $CaCl_2$ on sesquiterpene synthesis. ${\beta}$-eudesmol was apparent during cultivation except for when P. brumalis was grown on $MgSO_4$-free medium. These results demonstrated that $MgSO_4$ can specifically control the biosynthesis of ${\beta}$-eudesmol. Magnesium has been reported as a cofactor that binds to sesquiterpene synthase (Agger et al. 2008). Specifically, the $Mg^{2+}$ ions bind to two conserved metal-binding motifs. These metal ions complex to the substrate pyrophosphate, thereby promoting the ionization of the leaving groups of FPP and resulting in the generation of a highly reactive allylic cation. Effect of magnesium source on the sesquiterpene biosynthesis was also identified via analysis of the concentration of total carbohydrates. Our current study offered further insight that fungal sesquiterpene biosynthesis can be controlled by nutrients. To profile the metabolites of P. brumalis, the cultures were extracted based on the growth curve. Despite metabolites produced during mycelia growth, there was difficulty in detecting significant changes in metabolite production, especially those at low concentrations. These compounds may be of interest in understanding their synthetic mechanisms in P. brumalis. The synthesis of terpene compounds began during the growth phase at day 9. Sesquiterpene synthesis occurred after growth was complete. At day 9, drimenol, farnesol, and mevalonic lactone (or mevalonic acid lactone) were identified. Mevalonic acid lactone is the precursor of the mevalonic pathway, and particularly, it is a precursor for a number of biologically important lipids, including cholesterol hormones (Buckley et al. 2002). Farnesol is the precursor of sesquiterpenoids. Drimenol compounds, bi-cyclic-sesquiterpene alcohols, can be synthesized from trans-trans farnesol via cyclization and rearrangement (Polovinka et al. 1994). They have also been identified in the basidiomycota Lentinus lepideus as secondary metabolites. After 12 days in the growth phase, ${\beta}$-elemene caryophyllene, ${\delta}$-cadiene, and eudesmane were detected with ${\beta}$-eudesmol. The data showed the synthesis of sesquiterpene hydrocarbons with bi-cyclic structures. These compounds can be synthesized from FPP by cyclization. Cyclic terpenoids are synthesized through the formation of a carbon skeleton from linear precursors by terpene cyclase, which is followed by chemical modification by oxidation, reduction, methylation, etc. Sesquiterpene cyclase is a key branch-point enzyme that catalyzes the complex intermolecular cyclization of the linear prenyl diphosphate into cyclic hydrocarbons (Toyomasu et al. 2007). After 20 days in stationary phase, the oxygenated structures eudesmol, elemol, and caryophyllene oxide were detected. Thus, after growth, sesquiterpenes were identified. Per these results, we showed that terpene metabolism in wood-rotting fungi occurs in the stationary phase. We also showed that such metabolism can be controlled by magnesium supplementation in the growth medium. In conclusion, we identified P. brumalis as a wood-rotting fungus that can produce sesquiterpenes. To mechanistically understand eudesmane-type sesquiterpene biosynthesis in P. brumalis, further research into the genes regulating the dynamics of such biosynthesis is warranted.

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