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.

Membrane-based CO2 capture is an energy-saving way to separate CO2 from N2 in post-combustion. Chabazite (Si-CHA) zeolites with a pore size of 0.37 nm × 0.42 nm are expected to separate CO2 from larger N2 (0.364 nm) by recognizing minute size differences. The pore mouth size on the Si-CHA zeolites outer surface was reduced via the chemical vapor deposition (CVD) to increase the molecular sieving effect by disfavoring the penetration of N2. The CVD process was conducted on CHA membranes to improve their CO2/N2 separation performance. Compared to the intact CHA membranes, the CO2/N2 max separation factor for CVD-treated CHA membranes increased by ~2.5 fold under dry conditions and by ~6.4 fold under wet conditions. It is noteworthy that the membrane kept its separation performance without degradation in the presence of H2O.

CoSi2 was formed through annealing of atomic layer deposition Co thin films. Co ALD was carried out using bis(N,N'-diisopropylacetamidinato) cobalt (Co(iPr-AMD)2) as a precursor and NH3 as a reactant; this reaction produced a highly conformal Co film with low resistivity (50 μΩcm). To prevent oxygen contamination, ex-situ sputtered Ti and in-situ ALD Ru were used as capping layers, and the silicide formation prepared by rapid thermal annealing (RTA) was used for comparison. Ru ALD was carried out with (Dimethylcyclopendienyl)(Ethylcyclopentadienyl) Ruthenium ((DMPD)(EtCp)Ru) and O2 as a precursor and reactant, respectively; the resulting material has good conformality of as much as 90% in structure of high aspect ratio. X-ray diffraction showed that CoSi2 was in a poly-crystalline state and formed at over 800˚C of annealing temperature for both cases. To investigate the as-deposited and annealed sample with each capping layer, high resolution scanning transmission electron microscopy (STEM) was employed with electron energy loss spectroscopy (EELS). After annealing, in the case of the Ti capping layer, CoSi2 about 40 nm thick was formed while the SiOx interlayer, which is the native oxide, became thinner due to oxygen scavenging property of Ti. Although Si diffusion toward the outside occurred in the Ru capping layer case, and the Ru layer was not as good as the sputtered Ti layer, in terms of the lack of scavenging oxygen, the Ru layer prepared by the ALD process, with high conformality, acted as a capping layer, resulting in the prevention of oxidation and the formation of CoSi2.

DLC 박막을 RF 플라즈마 화학증착법(PECVD)을 이용하여 CH4와 CO2기체로부터 합성하였다. 증착압력, CH4와 CO2가스의 조성비, 바이어스 전압(-VB) 등의 증착조건 변화에 따른 증착속도는 증착층의 두께를 알파스텝으로 측정하여 결정하였으며, 박막의 구조 변화에 따른 증착속도는 증착층의 두께를 알파스텝으로 측정하여 결정하였으며, 박막의 구조 변화는 FTIR 분광분석을 이용하여 분석을 행하였다. 이 연구로부터 얻은 실험 결과는 다음과 같다: 1) 증착속도는 증착압력 및 바이어스 전압의 증가에 따라 증가한다. 2)바이어스 전압 300V이상에서, CO2량 증가는 순증착속도를 증가 시킨다. 3) 순수한 CH4가스를 사용할 경우에는 바이어스전압(-VB)이 증가함에 따라 박막내 수소의 함량과 sp3/sp2비는 감소하는 경향을 나타낸다. 4)증착압력이 증가함에 따라 박막내 수소함량은 증가하며, sp3/sp2비는 감소한다. 5)50mTorr의 증착압력에 증착시, CH4-+Co2 혼합가스에서 이산화탄소의 부피분율에 따라서는 박막내 수소함량은 감소하며, sp3/sp2비는 증가한다.