• Bulletin of the Korean Chemical Society
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• 제35권8호
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• pp.2438-2442
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• 2014

A kinetic study is reported for $S_NAr$ reaction of 1-fluoro-2,4-dinitrobenzene (5a) and 1-chloro-2,4-dinitrobenzene (5b) with alkali-metal ethoxides (EtOM, M = Li, Na, K and 18-crown-6-ether complexed K) in anhydrous ethanol. The second-order rate constant increases in the order $k_{EtOLi}$ < $k_{EtO^-}$ < $k_{EtONa}$ < $k_{EtOK}$ < $k_{EtOK/18C6}$ for the reaction of 5a and $k_{EtOLi}$ < $k_{EtONa}$ < $k_{EtO^-$ < $k_{EtOK}$ < $k_{EtOK/18C6}$ for that of 5b. This indicates that $M^+$ ion behaves as a catalyst or an inhibitor depending on the size of $M^+$ ion and the nature of the leaving group ($F^-$ vs. $Cl^-$). Substrate 5a is more reactive than 5b, although the $F^-$ in 5a is ca. $10pK_a$ units more basic than the $Cl^-$ in 5b, indicating that the reaction proceeds through a Meisenheimer complex in which expulsion of the leaving group occurs after the rate-determining step (RDS). $M^+$ ion would catalyze the reaction by increasing either the nucleofugality of the leaving group through a four-membered cyclic transition state or the electrophilicity of the reaction center through a ${\pi}$-complex. However, the enhanced nucleofugality would be ineffective for the current reaction, since expulsion of the leaving group occurs after the RDS. Thus, it has been concluded that $M^+$ ion catalyzes the reaction by increasing the electrophilicity of the reaction center through a ${\pi}$-complex between $M^+$ ion and the ${\pi}$-electrons in the benzene ring.

• 한국진공학회:학술대회논문집
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• 한국진공학회 2000년도 제18회 학술발표회 논문개요집
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• pp.163-163
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• 2000

In this research, we used the ion irradiation technique which has an advantae in improving intentionally the properties of surface and interface in a non-equilibrium, instead of the conventional annealing method which has been known to improve the material properties in the equilibrium stat. Cu/Co multilayered films were prepared on SiN4/SiO2/Si substrates by the electron-beam evaporation for the Co layers and the thermal evaporation for the Cu layers in a high vacuum. The ion irradiation with a 80keV Ar+ was carried out at various ion doses in a high vacuum. Hysteresis loops of the films were investigated by magneto-optical polar Kerr spectroscopy at various experimental conditions. The change of atomic structure of the films before and after the ion irradiation was studied by glancing angle x-ray diffraction, and the intermixing between Co and Cu sublayers was confirmed by Rutherford backscattering spectroscopy. The surface roughness and magneto-resistance were measured by atomic force microscopy and with a four-point probe system, respectively. During the magneto-resistance measurement, we changed temperature and the direction of magnetization. From the results of experiments, we found that the change at the interfaces of the Cu/Co multilayered film induced by ion irradiation cause the change of magnetic properties. According to the change in hysteresis loop, the surface inplane component of magnetic easy axis was isotropic before the ion irradiation, but became anisotropic upon irradiation. It was confirmed that this change influences the axial behavior of magneto-resistance. Especially, the magneto-resistance varied in accordance with an external magnetic field and the direction of current, which means that magneto-resistance also shows the uniaxial behavior.

• 센서학회지
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• 제6권3호
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• pp.214-220
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• 1997

본 연구에서는 생화학 물질을 정량적으로 분석하기 위하여 소산장(Evanescent field) 흡수를 이용한 박막 광도파로형 칼륨이온센서를 제작하였다. 도파로는 Pyrex glass($26{\times}19{\times}1mm$, $n_{1}=1.485$ at 514nm, Ar laer ; Coherent 사 M532) 기판위에 RF sputtering법으로 Coming-7059 glass($n_{2}=1.588$, at 514nm, Ar laer ; Coherent사 M532) 2 종류의 박막 광도파로를 형성하였으며, 그 두께는 프리즘 결합법으로 측정한 결과 각각 $T_{1}=1.04{\mu}m$ 와 $T_{2}=1.41{\mu}m$ 였다. 칼륨이온 선택성의 이온감지막은 변색성 이온감응물질인 ETH 5294와 중성이온감응물질인 valinomycin을 poly(vinyl chloride-co-vinyl acetate-co-vinyl alcohol) ( 91 : 3 : 6 ) 공중합체 막내에 포괄법으로 고정화한 후 도파로 위에 스핀코팅법으로 제조하였다. 그리고, 센서의 특성을 평가하기 위해 감지막의 작용길이, 도파로의 두께 및 변색성 이온감응물질의 조성비 변화에 따른 감도 의존성을 조사하였다. 본 센서는 약 $1{\times}10^{-6}M\;{\sim}1.0\;M$의 넓은 측정범위를 가지며, 90%의 응답시간은 약 1분 이내의 빠른 응답특성을 나타내었다. 또한 분광분석법에 의한 투과광도법 및 광섬유를 이용한 optode형 센서를 제작하여 본 센서와 그 특성을 비교한 결과, 본 센서의 우수성을 알 수 있었다. 따라서 본 센서는 생화학 및 의용, 환경감시 분야 등에 응용 가능할 것으로 사료된다.

• 마이크로전자및패키징학회지
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• 제9권4호
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• pp.11-16
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• 2002

본 연구에서는 $SrBi_2Ta_2O_9$ (SBT)박막의 고속식각에 따른 잔류물질 및 식각 손상의 영향을 조사하였다. ICP-RIE (inductively coupled plasma reactive ion etching) 의 ICP power와 CCP(capacitively coupled plasma) power를 변화시키면서 고속식각에 따른 박막의 손상과 열화를 XPS 분석과 Capacitance-Voltage (C-V) 측정을 통하여 알아보았다. ICP와 CCP의 power가 증가함에 따라 식각율이 증가하였고 ICP power가 700 W, CCP power가 200 W 일때 식각율은 900$\AA$/min이었다. 강유전체의 건식식각에 있어서 문제점이 플라즈마에 의한 강유전체 박막의 열화인데 반응가스 $Ar/C1_2/CHF_3$를 20/14/2의 비율로 사용하고 ICP와 CCP power를 각각 700w와 200w로 사용하였을 때 전혀 열화되지 않는 강유전체 박막의 특성을 얻을 수 있었다. 본 연구 결과는 Metal-Ferroelectric-Semiconductor (MFS) 또는 Metal-Ferroelectric-Insulator-Semiconductor (MFIS) 구조를 가지는 단일 트랜지스터형 강유전체 메모리 소자를 만드는데 건식 식각이 응용될 수 있음을 보여준다

• 한국재료학회지
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• 제4권1호
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• pp.9-23
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• 1994

Multitarget bias cosputter deposition(MBCD)에 의해 저온($200^{\circ}C$)에서 NaCI(100)상에 정합$CoSi_2$를 성장시켰다. X-선회절과 투과전자현미경에 의해 증착온도와 기판 bias전압에 따른 각각 silicide의 상전이와 결정성을 관찰하였다. Metal induced crystallization(MIC) 과 self bias 효과에 의해 $200^{\circ}C$에서 기판전압을 인가하지 않은 경우에도 결정질 Si이 성장하였다. MIC현상을 이론 및 실험적으로 고찰하였다. 관찰된 상전이는 $Co_2Si \to CoSi \to Cosi_2$로서 유효생성열법칙에 의해 예측된 상전이와 일치하였다. 기판 bias전압 인가시 발생한 이온충돌에 의한 충돌연쇄혼합(collisional cascade mixing), 성장박막 표면의 in situ cleaning, 핵생성처(nucleation site)이 증가로 인하여 상전이, CoSi(111)우선방위, 결정성은 증착온도에 비해 기판bias전압에 더 큰 영향을 받았다. $200^{\circ}C$에서 기판 bias전압을 증가시킴에 따라 이온충돌에 의한 결정입성장이 관찰되었으며, 이를 이온충독파괴(ion bombardment dissociation)모델에 의해 해석하였다. $200^{\circ}C$에서의 기판 bias전압증가에 따른 결정성변화를 정량적으로 고찰하기 위해 Langmuir탐침을 이용하여 $E_{Ar},\; \alpha(V_s)$를 계산하였다.

• 대한치과보철학회지
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• 제30권2호
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• pp.135-154
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• 1992

This study was performed to analyze bond strength, the alterations of the interfaces between metal films which are populary used and considered to contribute to the chemical reaction with porcelain, according to constant ion- beam- mixing, and the relation between interfacial chemical reactions and bond strength in metal/porcelain specimens. For this study, three seperate metals : selected-gold, indium and tin were chosen ; each to be bonded to a seperate body porcelain. Bonding occurs when the metal is deposited to the body porcelain using a vacuum evaporator. The vacuum evaporator used $10^{-5}\sim10^{-6}$ Torr vacuum states for the evaporation of various metals (Au, Sn, In). Ion-beam-mixing of the porcelain/metal interfaces caused reactions when the Ar+ was implanted into thin films using a 80 KeV accelerator. These ion-beam-mixed specimens were then compared with an unmixed control group. An analysis of bond strength and ionic changes between the the metal and porcelain was performed by electron spectroscopy of chemical analysis (ESCA) and scratch test. The finding led to the following conclusions : 1. Light microscopic views of the scratch test : The ion-beam-mixed Au/porcelain specimen showed narrower scratched streams than the unmixed specimen. However, the Sn/porcelain, In/porcelain specimens showed no differences in the two conditions. 2. Acoustic emissions in scratch tests : The ion-mixed Au/porcelain, In/porcelain specimens showed signals closer to the metal/porcelain interfaces than unmixed specimens. Conversely, the ion-mixed Sn/porcelain specimen showed more critical signals in superficial portions than unmixed specimens. 3. After ion- beam-mixing, the Au/porcelain specimen showed apparently increased bond strength, and the In/porcelain specimen showed very slightly increased bond strength. However, the Sn/porcelain specimen showed no differences between ion mixed specimen and the unmixed one. 4. ESCA analysis : The ion-beam-mixed Au/porcelain specimen showed a higher peak separated value (4.3eV) than that of the unmixed specimen(3.65eV), the ion-beam-mixed In/porcelain specimen showed a higher peak separated value (9.43eV) than that of the unmixed specimen(7.6eV) and the ion-beam-mixed Sn/porcelain specimen showed a higher peak separated value (8.79eV) than that of the unmixed specimen(8.5eV). 5. Interfacial changes were observed in the ion-mixed Au/porcelain, In/porcelain and Sn/porcelain specimens. Especially, significant interfacial changes were measured in the ion- mixed Sn/porcelain specimen. Tin dioxide(SnO2) and a combination of pure tin and tin dioxide (Sn+SnO2) were produced. 6. In the Au/porcelain specimen, the interfacial chemical reaction showed increased bond strength between gold and porcelain substrate. But, in the In/porcelain, Sn/porcelain specimens, interfacial chemical reactions did not affected the bond strength between metal and porcelain substrate. Especially, bonding strength on the ion mixed Sn/porcelain specimen showed the least amount of difference.

• 마이크로전자및패키징학회지
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• 제8권3호
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• pp.49-53
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• 2001

유도결합형 플라즈마 (ICP-RIE) 장치를 이용하여 SBT ($SrBi_2Ta_2O_9$)/Si의 수직식각 실험을 하였다. 이와 같은 실험의 목적은 수직 단면구조의 강유전체 gate구조 및 capacitor 제조에 있어서 유효면적을 확보하고 parasitic effect를 최소화 하는 기술이 우수한 소자 특성을 얻기 위해 매우 중요한 기술이기 때문이다. $Ar/C1_2$를 반응가스로 사용하였으며 $Ar/C1_2$유량비를 각각 1, 0.8, 0.6, 0.4로 바꾸어 가면서 각 유량비에 대해 RF power를 700, 600, 500W로 변화시키는 동안 DC power를 각각 200, 150, 100, 50 W로 변화시키면서 식각 실험을 하였다. 식각조건 변화에 따른 수직 및 수평 식각율, 선택식각율, 감광막의 보호성, 리소그라피 조건에 따른 식각율 및 식각단면 구조의 특성, 식각율 변화에 따른 패턴 크기의 변화, SBT의 식각 단면 특성 등을 조사하였다. $Ar/C1_2$유량비가 0.8, RF power 700 W, DC power 200 W 일 때 식각속도는 1050 A/min으로 최적의 식각율을 확인하였다. 그리고 주사전자현미경의 관찰 결과 수 적도는 $82^{\circ}C$ 정도로 매우 양호함을 알 수 있었다.

• 한국진공학회지
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• 제6권S1호
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• pp.96-109
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• 1997

In order to simulate the corrosion behavior of Zr-4 alloy in pressurized water reactors it was implanted (or bombarded) with 190ke V $Zr^+\; and \;Ar^+$ ions at liquid nitrogen temperature and room temperature respectively up to a dose of $5times10^{15} \sim 8\times10^{16} \textrm{ions/cm}^2$ The oxidation behavior and electrochemical vehavior were studied on implanted and unimplanted samples. The oxidation kinetics of the experimental samples were measured in pure oxygen at 923K and 133.3Pa. The corrosion parameters were measured by anodic polarization methods using a princeton Applied Research Model 350 corrosion measurement system. Auger Electron Spectroscopy (AES) and X-ray Photoelectric Spectroscopy (XPS) were employed to investigate the distribution and the ion valence of oxygen and zirconium ions inside the oxide films before and after implantation. it was found tat: 1) the $Zr^+$ ion implantation (or bombardment) enhanced the oxidation of Zircaloy-4 and resulted in that the oxidation weight gain of the samples at a dose of $8times10^{16}\textrm{ions/cm}^2$ was 4 times greater than that of the unimplantation ones;2) the valence of zirconium ion in the oxide films was classified as $Zr^0,Zr^+,Zr^{2+},Zr^{3+}\; and \;Zr^{4+}$ and the higher vlence of zirconium ion increased after the bombardment ; 3) the anodic passivation current density is about 2 ~ 3 times that of the unimplanted samples; 4) the implantation damage function of the effect of ion implantation on corrosion resistance of Zr-4 alloy was established.

• 한국진공학회:학술대회논문집
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• 한국진공학회 1998년도 제14회 학술발표회 논문개요집
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• pp.133-133
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• 1998

In the thin film alloy formation of the transition metals ion-beam-mixing technique forms a metastable structure which cannot be found in the arc-melted metal alloys. Sppecifically it is well known that the studies about the electronic structure of ion-beam-mixed alloys pprovide the useful information in understanding the metastable structures in the metal alloy. We studied the electronic change in the ion-beam-mixed ppt-Ct alloys by XppS and XANES. These analysis tools pprovide us information about the charge transfer in the valence band of intermetallic bonding. The multi-layered films were depposited on the SiO2 substrate by the sequential electron beam evapporation at a ppressure of less than 5$\times$10-7 Torr. These compprise of 4 ppairs of ppt and Cu layers where thicknesses of each layer were varied in order to change the alloy compposition. Ion-beam-mixing pprocess was carried out with 80 keV Ae+ ions with a dose of $1.5\times$ 1016 Ar+/cm2 at room tempperature. The core and valence level energy shift in these system were investigated by x-ray pphotoelectron sppectroscoppy(XppS) pphotoelectrons were excited by monochromatized Al K ａ(1486.6 eV) The ppass energy of the hemisppherical analyzer was 23.5 eV. Core-level binding energies were calibrated with the Fermi level edge. ppt L3-edge and Cu K-edge XANES sppectra were measured with the flourescence mode detector at the 3C1 beam line of the ppLS (ppohang light source). By using the change of White line(WL) area of the each metal sites and the core level shift we can obtain the information about the electrons pparticippating in the intermetallic bonding of the ion-beam-mixed alloys.

• 한국표면공학회지
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• 제53권3호
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• pp.116-123
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• 2020

Ion beam irradiation induces self-organization of nanostructure on the surface of polymer film. We show that the incident angle of Ar ions on polyethylene naphthalate(PEN) film changes self-organized nanostructure. PEN film was irradiated by argon ion beams with the ion incident angle of 0°, 30°, 45°, 60°, and 80°. Nanostructure was altered from dimple to ripple structure as the angle increases. The ripple structure changed to pillar structure after 60°due to that the shallow incident angle increased the ion energy transfer per depth up to 50 eV/Å, which value could induce excessive surface heating and oligomer formation reacting as a physical mask for anisotropic etching. And quantitative analysis of the nanostructures was adapted by using ABC model and fractal dimension theory.