• 한국자동차공학회논문집
• /
• 제24권3호
• /
• pp.302-309
• /
• 2016

Urea-SCR system is currently regarded as promising NOx reduction technology for diesel engines. SCR system has to achieve maximal NOx conversion in combination with minimal $NH_3$ slip. In this study, model based open loop control for urea injection was developed and assessed in the European Transient Cycle (ETC) for heavy duty diesel engine. On the basis of the transient modeling, the kinetic parameters of the $NH_3$ adsorption and desorption are calibrated with the experimental results performed over the zeolite based catalyst. $NH_3$ storage or surface coverage of SCR catalyst can not be measured directly and has to be calculated, which is taken into account as a control parameter in this model. In order to reduce $NH_3$ slip while maintaining NOx reduction, $NH_3$ storage control algorithm was applied to correct the basic urea quantity. If the actual $NH_3$ surface coverage is higher than the maximal $NH_3$ surface coverage, the urea injection quantity is significantly reduced in the ETC cycle. By applying this logic, the resulting $NH_3$ slip peak can be avoided effectively. With optimizing the kinetic parameters based on standard SCR reaction, it suggests that a simplified, less accurate model can be effective to evaluate the capability of model based control in the ETC cycle.

• 한국자동차공학회논문집
• /
• 제14권3호
• /
• pp.125-132
• /
• 2006

Transient kinetics of $NH_3$ adsorption/desorption and of SCR(selective catalytic reduction) of NO with $NH_3$ were studied over vanadium based catalysts, such as $V_2O_5/TiO_2$ and $V_2O_5-WO_3/TiO_2$. In the present catalytic reaction process, NO adsorption is neglected while $NH_3$ is strongly chemisorbed on the catalytic surface. Accordingly, it is ruled out the possibility of a reaction between strongly adsorbed $NH_3$ and NO species in line with the hypothesis of an Eley-Rideal mechanism. The present kinetic model assumes; (1) non-activated $NH_3$ adsorption, (2) Temkin-type $NH_3$ coverage dependence of the desorption energy, (3) non-linear dependence of the SCR reaction rate on the $NH_3$ surface coverage. Thus, the surface heterogeneity for adsorption/desorption of $NH_3$ is taken into account in this model. The present study extends the pure chemical kinetic model based on a powdered-phase catalytic system to the chemico-physical one applicable to a realistic monolith reactor.

• 한국진공학회:학술대회논문집
• /
• 한국진공학회 2012년도 제42회 동계 정기 학술대회 초록집
• /
• pp.265-265
• /
• 2012

The adsorption of molecular $NH_3$ on rutile $TiO_2(110)-1{\times}1$ surfaces was investigated using a temperature-programmed desorption (TPD) technique combined with a molecular beam apparatus. A quantitative investigation into the TPD spectra of $NH_3$ was made for $NH_3$ adsorbed on two kinds of rutile $TiO_2(110)-1{\times}1$ surfaces with the oxygen vacancy ($V_O$) concentration of ~0% (p-$TiO_2(110)$) and ~5% (r-$TiO_2(110)$), respectively. On both surfaces, non-dissociative adsorption of $NH_3$ was inferred from a quantitative analysis on the amount of adsorbed $NH_3$ and those desorbed. With increasing coverage, the monolayer desorption feature shifted from 400 K toward lower temperatures until it saturates at 160 K, suggesting a repulsive nature in the interaction between $NH_3$ molecules. At the very low coverage regime, the desorption features were found to extend up to 430 K and 400 K on p-$TiO_2(110)$ and p-TiO(110), respectively. As a result, the saturation coverage of monolayer of $NH_3$ was higher on the p-$TiO_2(110)$ surface than on the p-TiO(110) by about 10%. The desorption energy ($E_d$) of $NH_3$ obtained by inversion of the Polanyi-Wigner equation indicated that the difference between the $E_d$'s of $NH_3$ (that is, $E_d(on\;p-TiO_2(110)$) - $E_d$(on p-TiO(110)) was 14 kJ/mol at ${\theta}(NH_3)=0$ and decreased to 0 as the coverage approached to a monolayer. The observed adsorption behavior of $NH_3$ was interpreted using an interaction model between $NH_3$ and surface defects on $TiO_2$ such as VO's and $Ti^{3+}$ interstitials.

• 한국진공학회:학술대회논문집
• /
• 한국진공학회 2012년도 제42회 동계 정기 학술대회 초록집
• /
• pp.280-280
• /
• 2012

We examined ammonia diffusion on the surface of amorphous ice film through the measurement of decreasing residual quantity of $NH_3$ molecules compared to $H_2O$. The populations of $NH_3$ molecules on the surface of amorphous ice were monitored by using the techniques of temperature programmed reactive ion scattering (TPRIS) method. The ratio of intensity between ammonia and water was examined as a function of time at controlled temperature. When ammonia molecules were externally added onto an ice film at a temperature of 80 K, ammonia coverage with regard to ice was 0.12-0.16 ML. The intensity of ammonia molecules on the surface of ice decreased as time increased and the extent of decreased intensity of ammonia increased as controlled temperature increased. Moreover, energy barrier was estimated to be $51kJmol^{-1}$ on amorphous ice film. The results of the experiment indicate that ammonia molecules have a property of vertical diffusion into amorphous ice and the energy barrier of ammonia diffusion into bulk of ice is higher than that of hydrogen bonding.

• 한국재료학회:학술대회논문집
• /
• 한국재료학회 2010년도 춘계학술발표대회
• /
• pp.35.1-35.1
• /
• 2010

The Cu(In,Ga)Se2(CIGS) thin film solar cells have been achieved until almost 20% efficiency by NREL. These solar cells include chemically deposited CdS as buffer layer between CIGS absorber layer and ZnO window layer. Although CIGS solar cells with CdS buffer layer show excellent performance, many groups made hard efforts to overcome its disadvantages in terms of high absorption of short wavelength, Cd hazardous element. Among Cd-free candidate materials, the CIGS thin film solar cells with Zn compound buffer layer seem to be promising with 15.2%(module by showa shell K.K.), 18.6%(small area by NREL). However, few groups were successful to report high-efficiency CIGS solar cells with Zn compound buffer layer, compared to be known how to fabricate these solar cells. Each group's chemical bah deposition (CBD) condition is seriously different. It may mean that it is not fully understood to grow high quality Zn compound thin film on the CIGS using CBD. In this study, we focused to clarify growth mechanism of chemically deposited Zn compound thin film on the CIGS, especially. Additionally, we tried to characterize junction properties with unfavorable issues, that is, slow growth rate, imperfect film coverage and minimize these issues. Early works reported that film deposition rate increased with reagent concentration and film covered whole rough CIGS surface. But they did not mention well how film growth of zinc compound evolves homogeneously or heterogeneously and what kinds of defects exist within film that can cause low solar performance. We observed sufficient correlation between growth quality and concentration of NH3 as complex agent. When NH3 concentration increased, thickness of zinc compound increased with dominant heterogeneous growth for high quality film. But the large amounts of NH3 in the solution made many particles of zinc hydroxide due to hydroxide ions. The zinc hydroxides bonded weakly to the CIGS surface have been removed at rinsing after CBD.

• 한국반도체및디스플레이장비학회:학술대회논문집
• /
• 한국반도체및디스플레이장비학회 2002년도 추계학술대회 발표 논문집
• /
• pp.14-19
• /
• 2002

In this study, as Cu diffusion barrier, tantalum nitrides were successfully deposited on Si(100) substrate and SiO2 by plasma assisted atomic layer deposition(PAALD) and thermal ALD, using pentakis (ethylmethlyamino) tantalum (PEMAT) and $NH_3$ as precursors. The TaN films were deposited on $250^{\circ}$C by both method. The growth rates of TaN films were $0.8{\AA}$/cycle for PAALD and $0.75{\AA}$/cycle for thermal ALD. TaN films by PAALD showed good surface morphology and excellent step coverage for the trench with an aspect ratio of h/w - $1.8 : 0.12 \mu\textrm{m}$ but TaN films by thermal ALD showed bad step coverage for the same trench. The density for PAALD TaN was $11g/\textrm{cm}^3$ and one for thermal ALD TaN was $8.3g/\textrm{cm}^3$. TaN films had 3 atomic % carbon impurity and 4 atomic % oxygen impurity for PAALD and 12 atomic % carbon impurity and 9 atomic % oxygen impurity for thermal ALD. The barrier failure for Cu(200nm)/TaN(l0nm)/$SiO_2(85nm)$/Si structure was shown at temperature above $700^{\circ}$C by XRD, Cu etch pit analysis.

• 반도체디스플레이기술학회지
• /
• 제2권2호
• /
• pp.5-8
• /
• 2003

In this study, as Cu diffusion barrier, tantalum nitrides were successfully deposited on Si(100) substrate and $SiO_2$ by plasma assisted atomic layer deposition(PAALD) and thermal ALD, using pentakis (ethylmethlyamino) tantalum (PEMAT) and NH$_3$ as precursors. The TaN films were deposited at $250^{\circ}C$ by both method. The growth rates of TaN films were 0.8${\AA}$/cycle for PAALD and 0.75${\AA}$/cycle for thermal ALD. TaN films by PAALD showed good surface morphology and excellent step coverage for the trench with an aspect ratio of h/w -1.8:0.12 mm but TaN films by thermal ALD showed bad step coverage for the same trench. The density for PAALD TaN was 11g/cmand one for thermal ALD TaN was 8.3g/$cm^3$. TaN films had 3 atomic % carbon impurity and 4 atomic % oxygen impurity for PAALD and 12 atomic % carbon impurity and 9 atomic % oxygen impurity for thermal ALD. The barrier failure for Cu(200 nm)/TaN(10 nm)/$SiO_2$(85 nm)/ Si structure was shown at temperature above $700^{\circ}C$ by XRD, Cu etch pit analysis.

• Electronic Materials Letters
• /
• 제14권6호
• /
• pp.700-711
• /
• 2018

CdS synthesized by the chemical bath method at $70^{\circ}C$, has been used as an electron transport layer in the planar structure of the perovskite solar cells. A two-step spin process produced a mixed halide perovskite of $CH_3NH_3PbI_{3-x}Cl_x$ and a mixture of $PbCl_2$ and $PbI_2$ was deposited on CdS, followed by a sub-sequential reaction with MAI ($CH_3NH_3I$). The added $PbCl_2$ to $PbI_2$ in the first spin-step affected the structure, orientation, and shape of lead halides, which varied depending on the content of Cl. A small amount of Cl enhanced the surface morphology and the preferred orientation of $PbI_2$, which led to large and uniform grains of perovskite thin films. In contrast, the high content of Cl produces a new phase PbICl in addition to $PbI_2$, which leads to the small and highly uniform grains of perovskites. An improved surface coverage of perovskite films with the large and uniform grains maximized the performance of perovskite solar cells at 0.1 molar ratio of $PbCl_2$ to $PbI_2$. The depth profiling of elements in both lead halide films and mixed halide perovskite films were measured by Rutherford backscattering spectroscopy, revealing the distribution of chlorine along with the thickness, and providing the basis for the mechanism for enhanced preferred orientation of lead halide and the microstructure of perovskites.

• 한국재료학회지
• /
• 제8권5호
• /
• pp.377-382
• /
• 1998

Ti[N ($C_{2}$$H_{5}$ $CH_{3}$)$_{2}$]$_{4}$ [tetrakis(ethylmethylammino)titanium.TEMAT]와 $NH_{3}$를 반응가스로 하여 각각 펄스(pulse) 형태로 시분할 주입되는 새로운 박막 증착방법(이하 Cycle-CVD라 함)을 이용하여 TiN박막이 $SiO_2$.기판위에 증착되었다.Cycle-CVD에서 반을로 내로 주입되는 반응가스와 Ar가스는 TEAM 펄스, Ar 펄스,$NH_{3}$펄스, Ar 펄스의 순서로 시분할주입되었고, 이렇게 차례대로 주입되는 4개의 펄스를 하나의 cycle로 규정하고, Cycle-CVD는 이러한 cycle이 연속하여 반복적으로 주입되도록 설계되었다. 기판온도가 $170^{\circ}C$-$210^{\circ}C$에서는 atomic layer deposition(ALD)특성을 보였고, $200^{\circ}C$에서 충분한 반응가스의 펄스시간 후에 cycle당 증착된 박막의 두께가 0.6nm/cycle로 포화되는 양상을 보여주었는데, 이는 cycle당 증착된 TiN 박막의 두께가 1.6 monolayer(ML)/cycle에 해당된다. 이와 같이 반등가스의 흡착을 이용ㅇ하여 TiN이 제한된 표면반응만에 의하여 ALD 기구에 의해 증착이 이루어지므로 TiN 박막의 두께는 단지 cycle 횟수만으로 정확하게 제어할 수 있었고, 우수한 step coverage 특성을 얻었다. 또한 반응가스간의 기상반응을 방지함으로써 입자의 발생을 억제할 수 있었고, 상대적으로 낮은 온도임에도 불구하고 4at% 이하의 낮은 탄소함량을 갖는 양호한 특성을 보여주었다.

• 대한전자공학회논문지SD
• /
• 제37권6호
• /
• pp.43-49
• /
• 2000

ALE(atomic layer epitaxy)법을 이용하여 (100)면의 Si 기판위에 TiN 박막을 증착하였다. 증착된 TiN 박막을 XRD, 4-point probe, AFM, AES, SEM등의 장비를 사용하여 분석하였다. ALE법에 의한 TiN의 증착을 위한 반응 전구체(precusor)로는 TEMAT(tetrakis (ethylmethylamino)titanium)와 반응 가스로는 $NH_3$를 사용하였다. 표면 포화반응을 형성하기 위해 각 반응 기체는 TEMAT-$N_2-NH_3-N_2$의 순서로 교대로 반응로에 주입하였다. 그 결과 TiN 박막은 150 ~ 220 $^{\circ)C$에서 자기 제어 성장(self-limiting growth) 기구에 의한 박막 증착 특성을 보였다. 증착된 TiN 박막은 증착율이 4.5 ${\AA}$/ cycle로 일정하였고, 비정질 (amorphous)의 구조를 보였다. 박막의 저항율과 표면 평균 거칠기는 210~230${\mu}{\Omega}{\cdot}$cm와 7.9~9.3${\AA}$로 측정되었다. TiN 박막을 2000 ${\AA}$의 두께로 증착하였을 때, 폭이 0.43${\mu}$m이고 단차비 (aspect ratio)가 6인 트렌치 구조에서 매우 우수한 단차피복성을 보였다.