As the limitations of Moore’s Law become evident, there has been growing interest in advanced packaging technologies. Among various 3D packaging techniques, Cu-SiO2 hybrid bonding has gained attention in heterogeneous devices. However, certain issues, such as its high-temperature processing conditions and copper oxidation, can affect electrical properties and mechanical reliability. Therefore, we studied depositing only a heterometal on top of the Cu in Cu-SiO2 composite substrates to prevent copper surface oxidation and to lower bonding process temperature. The heterometal needs to be deposited as an ultra-thin layer of less than 10 nm, for copper diffusion. We established the process conditions for depositing a Co film using a Co(EtCp)2 precursor and utilizing plasma-enhanced atomic layer deposition (PEALD), which allows for precise atomic level thickness control. In addition, we attempted to use a growth inhibitor by growing a self-assembled monolayer (SAM) material, octadecyltrichlorosilane (ODTS), on a SiO2 substrate to selectively suppress the growth of Co film. We compared the growth behavior of the Co film under various PEALD process conditions and examined their selectivity based on the ODTS growth time.

1,3-다이옥솔란은 용매, 전해질 및 시약으로서 화학, 페인트 및 제약 산업에서 광범위한 관심을 받고 있는 화합물 이다. 1,3-dioxolane은 주로 독성, 발암성, 폭발성, 자동 인화성이 없으며 다기능성을 가지고 있어, 대부분의 유기 및 수성 용 매 조건에서 우수한 용해성을 가져 고분자 전구체로서 사용된다. 최근 몇 년 동안 이 물질은 배가스 및 천연 가스 혼합물에 서 CO2를 분리하기 위한 CO2 선택적 고분자 전구체로서 점점 더 많은 관심을 받고 있다. Poly(1,3-dioxolane) (PDXL)은 폴 리에틸렌 옥사이드(PEO)보다 높은 에테르 산소 함량을 가지고 있으며, 이는 극성 에테르 산소 그룹이 CO2에 대해 강한 친화 력을 나타내기 때문에 우수한 막 CO2/N2 분리 특성을 보인다. 따라서 PDXL 기반 분리막은 비극성(N2, H2 및 CH4) 가스에 대해 탁월한 CO2 용해도 선택성을 보인다. 그러나 PEO와 마찬가지로 PDXL의 극성기는 고분자 사슬의 밀집도를 증가시키고 고분자 결정화를 유발하여 기체 투과도를 감소시켜 이에 대한 개선이 필요하다. 이 논문에서는 기체 분리 응용 분야에서 PDXL기반 고분자막의 최근 발전과 한계에 대해 알아보고자 한다. 또한 CO2 분리 공정에서 1,3-dioxolane 기반 고분자의 한 계를 극복하기 위한 몇 가지 분자 설계방안에 대해 다루어 보기로 한다.

기체분리막을 이용한 바이오가스 및 천연가스 등의 CH4 고질화 공정은 타 공정에 비해 경제적이라는 장점이 있지만 필수적으로 CH4 손실이 발생하는 단점이 있다. 이는 CO2에 의한 가소화현상으로 CH4의 투과도가 증가하기 때문이다. 이러한 현상을 개선하고자 CO2 가소화에 대한 영향이 적은 Cellulose계열의 고분자를 이용하여 고선택도 멤브레인을 제막하였으며, 이를 이용하여 CH4 고질화를 위한 연구를 하였다. CO2, CH4, N2, O2 등 단일가스를 이용하여 CA기반의 8종의 고선택도 중공사막에 선택도와 투과도를 측정하였다. CO2/CH4 혼합가스 분리 테스트를 수행하였다.

고분자 전해질 연료전지의 연료에 포함된 일산화탄소의 선택적 산화를 위하여, 귀금속 촉매를 대체하기 위한 CuO-CeO2 복합 산화물 촉매를 졸-겔법과 공침법으로 제조하였다. 졸-겔법으로 촉매 제조 시 Cu/Ce의 비와 가수분해 비를 변화시켰다. 제조한 촉매의 활성은 귀금속 촉매(Pt/γ-Al2O3)와 비교하였다. Cu/Ce의 비를 변화시키면서 제조한 촉매 중 Cu/Ce의 비가 4:16인 촉매가 가장 높은 CO 전환율(90%)과 선택도(60%)를 나타내었다. 촉매의 제조에서 가수분해 비가 증가할수록 촉매 표면적이 증가하였고, 아울러 촉매 활성 또한 증가하였다. 공침법으로 제조한 촉매와 1wt% Pt/γ-Al2O3 촉매의 가장 높은 CO 전환율은 각각 82% 및 81%인 반면, 졸-겔법으로 제조한 촉매의 경우는 90%가 얻어졌다. 이는 졸-겔법으로 제조한 촉매가 공침법으로 제조한 촉매나 귀금속 촉매보다 더 높은 촉매활성을 보임을 의미한다. CO-TPD 실험을 통하여, 낮은 온도(140℃)에서 CO를 탈착하는 촉매가 본 반응에서 더 높은 촉매활성을 보임을 알 수 있었다.

The mixed matrix membranes for CO2/N2 separation, which is composed of commercially available MgCO3 and amphiphilic comb polymer matrix based on poly(ethyleneglycol) behenyl ether methacrylate and poly(oxyethelene methacrylate) synthesized via a facile free radical polymerization, were fabricated. The use of a CP improved the dispersion of the MgCO3 in ethanol due to the specific interaction between CP and MgCO3. The MMMs were characterized using scanning electron microscopy(SEM), high-resolution transmission electron microscopy(HR-TEM), and wide-angle X-ray scattering (WAXS). The best performance of gas separation for CP/MgCO3 MMM was shown in the case of 45wt% MgCO3 with the highest CO2 /N2 selectivity(93.8) and good CO2 permeance (30.9GPU). This performance of this CP/MgCO3 MMM is higher than other MgCO3 commercially available MMMs.

A cost-effective, easy method for enhancing the CO2 permeance and CO2/N2 selectivity of mixed matrix membranes (MMMs) was fabricated using commercially available MgCO3 crystals. The MgCO3 crystals were homogenously dispersed in polymer matrices via mechanical stirring to prepare MMMs. In particular, an amphiphilic comb polymer (CP) consisting of poly(ethylene glycol) behenyl ether methacrylate (PEGBEM) and poly(oxyethylene methacrylate) (POEM) was shown to be ideal matrix because of the interactions between its carbonyl oxygen atoms and MgCO3. Through SEM, HR-TEM, WAXS, DSC, FT-IR, N2 adsorption-desorption isotherm measurements and Raman spectroscopies, the MgCO3 and CP/MgCO3 hybrids were characterized. The CP/MgCO3 MMM with 45 wt% MgCO3 exhibited the highest CO2/N2 selectivity of 93.8 and CO2 permeance of 30.9 GPU.

There have been continuous research activities towards the designing of various separation technologies for the sequestration of CO2. Organic polymer membranes pay a great attention for its eco-friendliness, simple operation and energy-saving. Polymer membranes such as polyimides, polyethers, TRs and PIMs are well known for their high permeability and excellent mechanical, chemical, and thermal properties. However, the foremost challenge for these polymeric membrane materials is their enhanced selectivity to CO2 without sacrificing permeability. The selectivity problems would be overcome by ionic liquids (ILs), which lead to a considerable attention on RTILs-based sequestrations for CO2/N2 and CO2/CH4 separations. The current research trends based on RTIL polymer membranes, together with our original concept of applying RTIL to various polymeric structures will be presented.

Supercritical carbondioxide is very effective in removing oils from a variety of seed matrices, devoid of any appreciable amount of phospholipid content. However, the limited solubility of phosphalipids in supercritical carbondioxide leaves behind a potentially valuable by-product in spent seed matrix. Any phospholipid extraction process from the spent matrix must maintain the structure and the quality of phospholipids and must be compatible with the end use of the seed protein meal an animal feed or for human consumption. An initial supercritical carbondioxide extraction of soybean flakes was performed at 32 MPa and 80℃ to extract the oils, leaving the phospholipids in the deflatted soybean flakes, A second step was performed on the defatted soybean flake using Xeth=0.10, Varying the pressure from 175 MPa to 70.6 MPa and temperature from 60℃ to 80℃. For all supercritical carbon dioxide/ethanol mixture extractions, a fraction rich in phospholipids was obtained. The fractions extracted from defatted soybean flakes were dried and them redissolved in chloroform before HPLC-ELSD analysis. Quantitative and qualitative analysis of phospholipids on soybean seeds, defatted soybean flake, and different extracted phospholipid fractions was carried out, to ascertain the effect of extraction pressure and temperature.

분리층 두께가 5 μm이며 Si/Al 몰비가 1.5인 Na형 faujasite 제올라이트 분리막을 이차성장 공정에 의하여 제조하였고, 투과부에 13X 제올라이트 흡착제 충진 전후의 진공모드에서의 CO2/N2 분리거동을 CO2/N2 몰비가 1인 혼합기체에 대하여 30℃에서 평가하였다. 충진된 13X 제올라이트 흡착제는 CO2 투과도와 CO2/N2 선택도를 동시에 증진시켰다. 이 현상은 13X 제올라이트 흡착제 충진이 다공성 α-알루미나 지지체의 기공채널을 통한 CO2 탈출을 증진시킴으로써 faujasite 제올라이트/α-알루미나 상계면에서의 CO2 탈착을 증진시켰기 때문으로 설명되었다. 본 논문으로부터 흡착제와 분리막의 혼성화는 일반적으로 보여지는 선택도와 투과도의 역비례 관계를 획기적으로 개선할 방법임이 확인되었다.

To improve CO2 permselectivity, a modified silica membrane was prepared by chemical vapor deposition with tetraethoxysilane(TEOS)-ethanol-water, and TEOS-ethanol-water-HCI solution at 300-600℃. The silica was effectively deposited in the mesopores of a γ-alumina film coated on a porous α-alumina tube by evacuating the reactants through the porous wall. In this membrane, CO2 interacts, to some extent, with the pore wall, and CO2/N2 selectivity then exceeds the value of the Knudsen diffusion mechanism, while the membrane derived from TEOS alone has no CO2 selectivity. The silica membrane prepared from TEOS-ethanol-water-HC1 solution showed that CO2 permeance was 2.5×10-7㏖/s-1. m-2. Pa-1 at 30℃ and CO2/N2 selectivity was approximately 3. The CO2 permeance and selectivity was improved by enlarging the surface diffusion with modification of chemical affinity of the silica pores.

For effective CO2 separation using pore size controlled membrane, silica was deposited in the mesopores of a γ-alumina film by chemical vapor deposition of tetraethoxysilane (TEOS) and phenyl-substituted ethoxysilanes at 773-873K. The membranes prepared with phenyl-substituted ethoxysilanes were calcined to remove the phenyl group and control the pore size. The gas permselectivity of prepared membranes was evaluated by using H2, CO2, N2, CH4 and C3H8 single component and a mixture of CO2 and N2. The membranes produced using TEOS contained micropores having permselectivity only to hydrogen, but the phenyl-substituted ethoxysilane derived membranes possessed micropores which are recognizable molecules of CO2, N2 and CH4. In the diphenyldiethoxysilane-derived membrane, the CO2 permeance and selectivity of CO2/CH4 were 10-6 ㎥(STP)·m-2·s-1·kPa-1 and 11, respectively. Therefore, the use of phenyl-substituted ethoxysilane was effective in controlling micropore size for CO2 separation.