• Bulletin of the Korean Chemical Society
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• 제15권11호
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• pp.996-1000
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• 1994

Ab initio calculations with various basis sets have been carried out to investigate the geometries and ring inversion barrier of $R_2TiC_3H_6\;and\;R_2TiS_3$, R=Cp and Cl. Optimized geometries of $R_2TiC_3H_6$ showed the four membered ring was planar on Cs symmetry. However, $R_2TiS_3$ complexes were optimized to be stable in the puckered form. The smallest Basis III with STO-3G on Cp ligands gave reasonable results for the calculations of metallocene. The energy barrier for the ring inversion of metallacyclosulfanes, $Cp_2TiS_3$ was computed to be 8.72 kcal/mol at MP2 level. For the Cl system, we reproduced the molecular structure and ring inversion energy with Basis V.

• Bulletin of the Korean Chemical Society
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• 제15권8호
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• pp.658-662
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• 1994

Ab initio and extended Huckel calculations have been applied to discuss the electronic structure, ring inversion barrier, and geometry of the $Cp_2TiS_3$ compound. The deformation of four membered ring in the planar geometry is originated from a second-order Jahn-Teller distortion due to the small energy gap between HOMO and LUMO on the basis of extended Huckel calculations. The puckered $C_s$ geometry is stabilized by the interaction of the $x^2-y^2$ metal orbital with the hybrid orbital in sulfur. Ab initio calculations have been carried out to explore the ring inversion process for the model $Cl_2TiS_3$ compound. We have optimized $C_s$ and $C_{2v}$ structures of the model compound at the RHF level. The energy barriers for the ring inversion are sensitive to the used basis set. With 4-31$G^*$ for the Cl and S ligands, the barriers are computed to be 8.41 kcal/mol at MP2 and 8.02 kcal/mol at MP4 level.

• 대한화학회지
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• 제34권3호
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• pp.239-247
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• 1990

기체상 $S_N2$ 반응의 형태는 중성 2분자반응, 용매화반응, 이온반응 등으로 나눌 수 있으며, 메카니즘적으로 중성 2분자 반응은 retention 생성물을 만들며 이온반응은 inversion 생성물을 만든다. 한편 용매인 물 한 분자에 의하여 6- 중심 건이상태를 거치는 용매화반응의 경우는 친핵체(또는 이탈기)및 치환기에 의한 전자효과와 입체효과에 따라 두 생성물이 경쟁적으로 만들어진다. 여기에서 얻어진 결과를 이용하여 이온반응의 경우, 중앙 methly group을 매우 bulky 하게 하고 이탈기 능력을 크게 해줌과 동시에 음이온인 친핵체의 하전을 분산시켰을 때 inversion과 retention TS 사이의 에너지 차이가 아주 작게 나타났다. $S_N2$ 반응의 반응중심을 보다 더 큰 2주기 원소로 바꾸었을 때, 5가의 전이상태에 미치는 입체장애가 작아지므로 활성화에너지 장벽이 낮아진다. 반면, 같은 주기에서 원자의 크기가 작아지면 에너지 장벽은 올라간다. B원자의 경우 에너지 장벽이 가장 낮은데, 그것은 C와 N 원자보다도 더 크며 또한 4가의 전이상태를 이루므로 입체장애가 거의 무시되기 때문이다.

• 한국진공학회:학술대회논문집
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• 한국진공학회 2015년도 제49회 하계 정기학술대회 초록집
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• pp.209.2-209.2
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• 2015

Two dimensional layered materials, such as transition metal dichalcogenides (TMDs) family have been attracted significant attention due to novel physical and chemical properties. Among them, molybdenum disulfide ($MoS_2$) has novel physical phenomena such as absence of dangling bonds, lack of inversion symmetry, valley degrees of freedom. Previous studies have shown that the interface of metal/$MoS_2$ contacts significantly affects device performance due to presence of a scalable Schottky barrier height at their interface, resulting voltage drops and restricting carrier injection. In this study, we report a new device structure by using few-layer graphene as the bottom interconnections, in order to offer Schottky barrier free contact to bi-layer $MoS_2$. The fabrication of process start with mechanically exfoliates bulk graphite that served as the source/drain electrodes. The semiconducting $MoS_2$ flake was deposited onto a $SiO_2$ (280 nm-thick)/Si substrate in which graphene electrodes were pre-deposited. To evaluate the barrier height of contact, we employed thermionic-emission theory to describe our experimental findings. We demonstrate that, the Schottky barrier height dramatically decreases from 300 to 0 meV as function of gate voltages, and further becomes negative values. Our findings suggested that, few-layer graphene could be able to realize ohmic contact and to provide new opportunities in ohmic formations.

• 한국재료학회지
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• 제26권10호
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• pp.556-560
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• 2016

Using current-voltage (I-V) and capacitance-voltage (C-V) measurements, the electrical properties of Au and Cu Schottky contacts to n-Ge were comparatively investigated. Lower values of barrier height, ideality factor and series resistance were obtained for the Au contact as compared to the Cu contact. The values of capacitance showed strong dependence on the bias voltage and the frequency. The presence of an inversion layer at the interface might reduce the intercept voltage at the voltage axis, lowering the barrier height for C-V measurements, especially at lower frequencies. In addition, a higher interface state density was observed for the Au contact. The generation of sputter deposition-induced defects might occur more severely for the Au contact; these defects affected both the I-V and C-V characteristics.

• Bulletin of the Korean Chemical Society
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• 제33권12호
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• pp.4161-4164
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• 2012

Density functional MO calculations for the methylsilole anion of $[C_4H_4SiMe]^-$ and methylgermole anion of $[C_4H_4SiMe]^-$ at the B3LYP (full)/6-311+$G^*$ level (GAUSSIAN 94) were carried out and characterized by frequency analysis. The ground state structure for the methylsilole anion and methylgermole anion is that the methyl group is pyramidalized with highly localized structure. The difference between the calculated $C_{\alpha}-C_{\beta}$ and $C_{\beta}-C_{\beta}$ distances are 9.4 and 11.5 pm, respectively. The E-Me vector forms an angle of $67.9^{\circ}$ and $78.2^{\circ}$ with the $C_4E$ plane, respectively. The optimized structures of the saddle point state for the methylsilole anion and methylgermole anion have been also found as a planar with highly delocalized structure. The optimized $C_{\alpha}-C_{\beta}$ and $C_{\beta}-C_{\beta}$ distances are nearly equal for both cases. The methyl group is located in the plane of $C_4E$ ring and the angle between the E-Me vector and the $C_4E$ plane for the methylsilole anion and methylgermole anion is $2.0^{\circ}$ and $2.3^{\circ}$, respectively. The energy difference between the ground state structure and the transition state structure is only 5.1 kcal $mol^{-1}$ for the methylsilole anion. However, the energy difference of the methylgermole anion is 14.9 kcal $mol^{-1}$, which is much higher than that for the corresponding methylsilole monoanion by 9.8 kcal $mol^{-1}$. Based on MO calculations, we suggest that the head-to-tail dimer compound, 4, result from [2+2] cycloaddition of silicon-carbon double bond character in the highly delocalized transition state of 1. However, the inversion barrier for the methylgermole anion is too high to dimerize.

• 한국진공학회지
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• 제5권4호
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• pp.333-340
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• 1996

Cu 확산방지막으로서의 Tin의 특성을 면저항 특정, X선 회절 분석, SEM, AES, capacitance-voltage(C-V) 측정에 의하여 평가하고, Cu의 확산을 민감하게 알아내는 정도를 특성 평가 방법간에 비교하였다. 여러 가지 증착방법에 의하여 Cu/TiN/Ti/SiO2/Si 구조의 다층 박막시편을 제작하였으며, 이 시편을 10% H2/90% Ar분위기, 열처리 온도 500~$800{\circ}C$ 범위에서 2시간 동안 열처리하였다. TiN의 Cu 확산방지 효과가 소멸된 경우 Cu 박막 표면에서 불규칙한 모양의 spot을 관찰할 수 있었으며 outdiffusion된 Si를 검출할 수 있었다. MOS capacitor의 C-V 특성은 열처리 온도에 따라 급격하게 변화하였다. C-V 측정에서 inversion capacitance는 열처리 온도 500~$700^{\circ}C$범위에서 열처리 온도가 높아질수록 감소하다가 $800^{\circ}C$에서 크게 증가하였으며, 이러한 특성의 변화는 TiN을 통해서 $SiO_2$와 Si내로 확산된 Cu에 의하여 발생되는 것으로 생각된다.

• 센서학회지
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• 제31권4호
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• pp.271-277
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• 2022

We analyzed the effects of the interface trap on the output characteristics of an inversion mode n-channel GaN Schottky barrier (SB)-MOSFET based on the N_it distribution using TCAD simulation. As interface trap number density (N_it) increased, the threshold voltage increased while the drain current density decreased. Under N_it=5.0×10¹⁰ cm^-2 condition, the threshold voltage was 3.2 V for V_DS=1 V, and the drain current density reduced to 2.4 mA/mm relative to the non-trap condition. Regardless of the N_it distribution type, there was an increase in the subthreshold swing (SS) following an increase in N_it. Under U-shaped N_it distribution, it was confirmed that the SS varied depending on the gate voltage. The interface fixed charge (Q_f) caused an shift in the threshold voltage and increased the off-state current collectively with the surface trap. In summary, GaN SB-MOSFET can be a building block for high power UV optoelectronic circuit provided the surface state is significantly reduced.

• Bulletin of the Korean Chemical Society
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• 제26권9호
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• pp.1339-1343
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• 2005

The N-inversion energies and nucleophilic ring-opening reactions of N-substituted aziridine compounds are investigated using B3LYP/6-31+$G^*$ methods, where substituents (R) on the nitrogen atom has been H (1), Me (2), Ph (3), Bn (4), CHMePh (5), $CO_2Me$ (6), COPh (7) and $SO_2Ph$ (8). The N-inversion energy with X group are decreased as the following order: R = CHMePh (17.06 kcal/mol) $\gt$ Me (16.97) $\gt$ Bn (16.70) $\gt$ H (16.64) $\gt$ $SO_2Ph$ (12.18) $\gt$ Ph (8.91) $\gt$ COPh (5.75) $\gt$ $CO_2Me$ (5.48). For reactivity of the ring opening toward cyanide ion, the aziridine 6 (R=$CO_2Me$) is shown to be the most reactive one. During the ring opening of aziridine 6 by CN$^{\ominus}$, the torsional OCNC angle becomes near to $180^{\circ}$, where the geometry allows for the effective incorporation of electrons of the nitrogen atom to the C=O bond. It would be a possible driving force for nucleophilic ring opening reaction as well as decreasing the N-inversion energy barrier. Regarding to the regioselectivity, the orientation of nucleophile in ring opening reaction appears to be different in the case of 9 and 10. The results are discussed in terms of steric/electronic effect of the $C_2$-substituents.

• 통합자연과학논문집
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• 제6권2호
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• pp.65-70
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• 2013

1,1-Bis(n-butyl)-2,3,4,5-tetraphenyl-1-silacyclopentadiene (3) and 1,1-bis(t-butyl)-2,3,4,5-tetraphenyl-1-silacyclopentadiene (4) are synthesized from the reaction of the versatile silole dianion (2) with n-butyl bromide and t-butyl bromide. Reduction of (3) and (4) with an excess of lithium to give 1,1-bis(n-butyl)-2,5-dilithio-2,3,4,5-tetraphenyl-1-silacyclopenta-3-enide (6) and 1,1-bis(t-butyl)-2,5-dilithio-2,3,4,5-tetraphenyl-1-silacyclopenta-3-enide (7). $^{13}C$-NMR study of two 2,5-carbodianions (6 and 7) shows tert-carbanion at 73.18 and 78.12 ppm respectively. Two bulky tert-butyl groups in (7) increase the inversion barrier at the tert-carbanion, line broadenings of tert-butyl groups in $^1H$ and $^{13}C$-NMR spectrum are observed.