XPS를 이용한 Cu / TiN의 계면에 관한 연구

이연승(Youn-Seoung Lee),임관용(Kwanyong Lim),정용덕(Young-Duck Chung),최범식(Bum-Sik Choi),황정남(Chung-Nam Whang) 한국진공학회(ASCT) 1997 Applied Science and Convergence Technology Vol.6 No.4

XPS를 이용하여 공기 중에 노출된 TiN 박막과 상온 증착된 Cu사이의 계면에서의 화학적 반응과 전자 구조적인 변화를 조사하였다. Ti(2p), O(1s), N(1s), Cu(2p) core-level과 Cu LMM Auger line의 spectrum을 보면, Cu의 증착두께가 증가하여도 peak의 위치 뿐만 아니라 line shape이 전혀 변화하지 않는다. 그리고 XPS에 의한 valence bands를 보아도 전혀 변화가 없다. 이것은 공기 중에 노출된 TiN 박막과 Cu 사이의 계면에서 Cu 화합물의 어떠한 형태도 존재하지 않을 뿐만 아니라 전자 구조적인 면에서도 전혀 변화가 없음을 의미한다. 계면에서 Cu가 화학적 반응을 일으키지 않는 것은 계면접합력을 나쁘게 하는 요인이 된다. 우리는 계면에서의 화학 반응 또는 전자구조의 변화에 대한 연구를 통하여 Cu와 TiN 박막의 계면접합력을 이해할 수 있었다. A chemical reaction and electronic structure change at the interface between copper and titanium nitride were investigated by XPS. A thin Cu layer was deposited on a TiN substrate oxidized by exposure to air at room temperature. We observed the Ti(2p), O(1s), N(1s), Cu(2p) core-level, and Cu LMM Auger line spectra. With increasing of the thickness of Cu layer, these spectra do not show any changes in the line shape as well as in peak position. In addition, the valence band spectra in XPS do not show any changes, which indicates that Cu does not react with Ti, N, and O. This inreactivity of Cu might cause a poor adhesion between Cu and TiN.

XPS를 이용한 Cu / Polyimide의 계면에 관한 연구 : 고온에서 증착한 Cu의 초기성장과정(Ⅱ)

이연승(Youn-Seoung Lee),황정남(Chung Nam Whang) 한국진공학회(ASCT) 1998 Applied Science and Convergence Technology Vol.7 No.2

고온 (350℃)에서 polyimide 위에 증착한 Cu의 초기성장 과정과 Cu/polyimide 계면에서의 반응물 형성에 관하여 XPS를 이용하여 관찰하였다. Polyimide 위에 고온 중에서의 Cu 증착시, 상온에서와는 달리 초기에는 Cu-C-N complex가 먼저 형성되고, 다음에 Cu-N-O complex가 주가 되어 Cu/polyimide 계면을 형성하고, Cu의 증착두께가 증가함에 따라 Cu 산화물에서 서서히 metallic Cu로 성장하는 것을 볼 수 있었다. 그리고 반응물 형성 관점에서, Cu 고온 증착시에 형성된 Cu/polyimide의 계면이 상온에서 이루어진 계면보다 상당히 예리함을 볼 수 있었다. We investigated the initial growth mode of Cu deposited on polyimide at high temperature (350℃) using x-ray photoelectron spectroscopy. We could find that when Cu is sputter-deposited on the polyimide at high temperature, Cu-C-N complex is formed first, Cu-N-O complex and Cu-oxide are mainly formed successively, and then finally metallic Cu grows. In the chemical reaction point of view, the interface of Cu/polyimide at high temperature is than that at room temperature.

XPS를 이용한 Cu / Polyimide 계면에 관한 연구 : 상온에서 증착한 Cu의 초기성장과정(I)

이연승(Youn-Seoung Lee),황정남(Chung Nam Whang) 한국진공학회(ASCT) 1997 Applied Science and Convergence Technology Vol.6 No.3

상온에서 polyimide 위에 증착한 Cu의 초기성장 과정과 Cu/polyimide의 계면의 형태에 관하여 XPS를 이용하여 관찰하였다. Polyimide 위에 Cu가 증착됨에 따라, 초기단계에는 강한 결합의 Cu-N-O complex가 주가 되어 Cu/polyimide 계면을 형성하고, Cu의 증착두께가 증가함에 따라, 약한 결합의 Cu 산화물에서 서서히 metallic Cu로서 성장하는 것을 볼 수 있었다. 이상의 결과들을 통해, Cu/polyimide의 계면은 Cu-N-O complex와 Cu 산화물이 혼합되어 있는 형태이며 polyimide 표면에 가까울수록 Cu-N-O complex가 주가 되고, Cu 쪽에 가까울수록 Cu 산화물이 주가 되는 형태를 이루고 있다는 것을 알 수 있었다. We investigated the initial growth mode of Cu deposited on polyimide at room temperature using x-ray photoelectron spectroscopy. We could find that when Cu is sputter-deposited on the polyimide, Cu-N-O complex of strong interaction is mainly formed first, Cu-oxide of weak interaction is formed successively, and then finally metallic Cu grows. From these results, we could conclude that Cu/polyimide interface consists of Cu-N-O complex and Cu-oxide.

약알칼리탈지 용액에서의 구리 Seed 층의 전처리 효과

이연승,김성수,나사균,Lee, Youn-Seoung,Kim, Sung-Soo,Rha, Sa-Kyun 한국진공학회 2012 Applied Science and Convergence Technology Vol.21 No.1

Sputter 방식으로 증착된 구리 seed 층(구리 seed/Ti/Si) 위에 형성된 오염물 제거과정을 이해하기 위하여, 강력한 계면 활성능력을 가진 약알칼리 탈지제 Metex TS-40A 용액을 사용하여 담금(dipping) 시간에 따른 구리 seed 층 표면의 변화형상 및 변화상태를 조사 분석하였다. Field emission scanning electron microscope을 이용하여 TS-40A 용액에 전처리 후 구리 seed 표면 형상이 grain이 명확히 보일 정도로 변화하는 것을 관찰하였고, X-ray photoelectron spectroscopy를 이용하여 표면 처리된 Cu seed 표면의 화학구조 및 불순물 상태를 조사하였다. TS-40 용액에서의 dipping 시간 변화에 따른 효과는 거의 없었다. TS-40A 용액에 전처리한 후, 구리 seed 층 표면위의 많은 탄소성분이 제거되었고, 약간의 산소가 제거되었으며, O=C 및 $Cu(OH)_2$에 해당되는 피크들이 감소되는 것이 관측되었다. 하지만 표면에서 불순물 Si이 silicate 상태로 검출되었다. TS-40A 용액에 포함되어 있는 silicate 성분이 구리 seed 층과 반응하여 이 silicate 불순물이 구리 seed 표면에 형성된 것으로 보여진다. 약알칼리 탈지제 Metex TS-40A 용액을 사용한 전처리 과정을 통해, 구리 seed 표면 위의 O=C 및 $Cu(OH)_2$ 등의 제거에는 탁월한 효과를 보였으나, 불순물 silicate가 형성되었으므로 이 알칼리 탈지제를 사용한다면, 이후에 산세정 및 다른 세정과정을 거쳐 표면에 존재하는 silicate를 제거할 필요성이 있다. In order to understand a process of contaminants removal on surface of Cu seed layer (Cu seed/Ti/Si) by sputter deposition, we investigated the changed morphology and states of Cu seed surface after pretreatment in alkali degreasing Metex TS-40A solution according to dipping time. After TS-40A pretreatment, the surface morphology with clearer grains was observed by Field emission scanning electron microscope and the changed surface chemical states and impurities on surface of samples were checked by X-ray photoelectron spectroscopy. Dipping time in TS-40A solution had very little effect on surface of Cu seed layer. After pretreatment, much carbons and little oxygens on surface of Cu seed were eliminated and the decrease of peaks corresponded to O=C and $Cu(OH)_2$ was estimated. However, Si content (=silicate) was detected on sample surface. We think that the silicate impurity forms on Cu seed by chemical reaction of TS-40A solution included silicate component. By pretreatment of alkali degreasing Metex TS-40A solution, it showed an excellent effect in removal of O=C and $Cu(OH)_2$ on Cu seed layer, but the silicate was formed on surface of Cu seed. Therefore, another cleaning process such as acid cleaning is required for removal of this silicate in use of this alkali degreasing.

무전해 Ni 도금을 위한 양극 산화막위에 스크린 인쇄된 Ag 페이스트 패턴의 정밀도 개선

이연승,나사균,Lee, Youn-Seoung,Rha, Sa-Kyun 한국재료학회 2017 한국재료학회지 Vol.27 No.8

We used an etching process to control the line-width of screen printed Ag paste patterns. Ag paste was printed on anodized Al substrate to produce a high power LED. In general, Ag paste spreads or diffuses on anodized Al substrate in the process of screen printing; therefore, the line-width of the printed Ag paste pattern increases in contrast with the ideal line-width of the pattern. Smudges of Ag paste on anodized Al substrate were removed by neutral etching process without surface damage of the anodized Al substrate. Accordingly, the line-width of the printed Ag paste pattern was controlled as close as possible to the ideal line-width. When the etched Ag paste pattern was used as a seed layer for electroless Ni plating, the line width of the plated Ni film was similar to the line-width of the etched Ag paste pattern. Finally, in pattern formation by Ag paste screen printing, we found that the accuracy of the line-width of the pattern can be effectively improved by using an etching process before electroless Ni plating.

NH₄OH용액이 반도체 소자용 구리 박막 표면에 미치는 영향

이연승,노상수,나사균,Lee, Youn-Seoung,Noh, Sang-Soo,Rha, Sa-Kyun 한국재료학회 2012 한국재료학회지 Vol.22 No.9

We investigated cleaning effects using $NH_4OH$ solution on the surface of Cu film. A 20 nm Cu film was deposited on Ti / p-Si (100) by sputter deposition and was exposed to air for growth of the native Cu oxide. In order to remove the Cu native oxide, an $NH_4OH$ cleaning process with and without TS-40A pre-treatment was carried out. After the $NH_4OH$ cleaning without TS-40A pretreatment, the sheet resistance Rs of the Cu film and the surface morphology changed slightly(${\Delta}Rs:{\sim}10m{\Omega}/sq.$). On the other hand, after $NH_4OH$ cleaning with TS-40A pretreatment, the Rs of the Cu film changed abruptly (${\Delta}Rs:till{\sim}700m{\Omega}/sq.$); in addition, cracks showed on the surface of the Cu film. According to XPS results, Si ingredient was detected on the surface of all Cu films pretreated with TS-40A. This Si ingredient(a kind of silicate) may result from the TS-40A solution, because sodium metasilicate is included in TS-40A as an alkaline degreasing agent. Finally, we found that the $NH_4OH$ cleaning process without pretreatment using an alkaline cleanser containing a silicate ingredient is more useful at removing Cu oxides on Cu film. In addition, we found that in the $NH_4OH$ cleaning process, an alkaline cleanser like Metex TS-40A, containing sodium metasilicate, can cause cracks on the surface of Cu film.

3D패키지용 Via 구리충전 시 전류밀도와 유기첨가제의 영향

최은혜,이연승,나사균,Choi, Eun-Hey,Lee, Youn-Seoung,Rha, Sa-Kyun 한국재료학회 2012 한국재료학회지 Vol.22 No.7

In an effort to overcome the problems which arise when fabricating high-aspect-ratio TSV(through silicon via), we performed experiments involving the void-free Cu filling of a TSV(10~20 ${\mu}m$ in diameter with an aspect ratio of 5~7) by controlling the plating DC current density and the additive SPS concentration. Initially, the copper deposit growth mode in and around the trench and the TSV was estimated by the change in the plating DC current density. According to the variation of the plating current density, the deposition rate during Cu electroplating differed at the top and the bottom of the trench. Specifically, at a current density 2.5 mA/$cm^2$, the deposition rate in the corner of the trench was lower than that at the top and on the bottom sides. From this result, we confirmed that a plating current density 2.5 mA/$cm^2$ is very useful for void-free Cu filling of a TSV. In order to reduce the plating time, we attempted TSV Cu filling by controlling the accelerator SPS concentration at a plating current density of 2.5 mA/$cm^2$. A TSV with a diameter 10 ${\mu}m$ and an aspect ratio of 7 was filled completely with Cu plating material in 90 min at a current density 2.5 mA/$cm^2$ with an addition of SPS at 50 mg/L. Finally, we found that TSV can be filled rapidly with plated Cu without voids by controlling the SPS concentration at the optimized plating current density.

미소초점엑스선원 개발을 위한 전산모사

김성수,이연승,김도윤,고동섭,Kim, Sung-Soo,Lee, Youn-Seoung,Kim, Do-Yun,Ko, Dong-Seob 한국진공학회 2011 Applied Science and Convergence Technology Vol.20 No.6

MFX tube를 개발하기 위하여, MFX tube 내에서 전계방출음극으로부터 방출된 전자의 궤적을 SIMION 프로그램을 이용하여 전산모사하였다. 전자의 출발위치와 상관없이 emitter에서 방출된 전자빔을 한곳에 집중시킬 수 있는 optimum extractor voltage Ve가 존재한다는 것을 알아내었다. Extractor voltage Ve는 source voltage Vs에 따라 변하지만, 두 전압의 비율(Ve/Vs)는 항상 일정하고, 그 값은 99.4%였다. Source와 extractor에 인가된 전압의 비율(Ve/Vs)이 99.4%일 때, 교차점에서의 빔 직경은 $1.2{\mu}m$였다. MFXG의 초점 크기는 교차점에서의 beam diameter보다 작을 수 없기 때문에, 교차점에서의 beam diameter을 작게 할 수 있는 조건을 찾는 것은 중요하다. 따라서 위의 두 결과는 MFX tube의 개발에 있어서 매우 중요한 결과로 판단된다. To develop the MFX (Micro-Focus X-ray) tube, the trajectories of electrons emitted from the field emission cathode was simulated using SIMION program. Regardless of starting position of the electron in emitter, we found out the fact that there is the optimum extractor voltage Ve, which can focus the electron beam on one place. Extractor voltage Ve varies depending on the source voltage Vs, but the ratio of two voltages (Ve/Vs) is always constant, its value was 99.4%. When the ratio of two voltages (Ve/Vs) was 99.4%, the beam diameter in the cross-over point was $1.2{\mu}m$. Because the focal spot size in MFXG (Micro-Focus X-ray Generator) can not be less than the cross-over diameter within MFX tube, it is important to find out the conditions that can make a smaller beam diameter. Therefore, the above results is considered to be a very important ones in the development of the MFXG.

XRD와 XAS에 의한 TiO₂ 분말의 상분율 결정

나사균,이연승,Rha, Sa-Kyun,Lee, Youn Seoung 한국세라믹학회 2012 한국세라믹학회지 Vol.49 No.5

The crystallinity and phase ratio of anatase to rutile in $TiO_2$ were estimated by x-ray diffraction (XRD) and x-ray absorption spectroscopy (XAS). Traditionally, the structural characterization of $TiO_2$ powders has been carried out by XRD techniques, which are comparatively easy in use and analysis. However, materials with amorphous phase, nano-sized or nano-structured crystallinities cannot be fully characterized by XRD because XRD analysis has a limit for abnormal contributions of the nano-crystal such as the surface contribution. From the comparison with the experimental and calculated Ti K-edge XAS spectra, we found the possibility of efficient estimation in the crystalinites and the phase ratio of anatase to rutile for nano-sized $TiO_2$ mixture.

인쇄회로기판상의 금속 배선을 위한 구리 도금막 형성 : 무전해 중성공정

조양래,이연승,나사균,Cho, Yang-Rae,Lee, Youn-Seoung,Rha, Sa-Kyun 한국재료학회 2013 한국재료학회지 Vol.23 No.11

We investigated the characteristics of electroless plated Cu films on screen printed Ag/Anodized Al substrate. Cu plating was attempted using neutral electroless plating processes to minimize damage of the anodized Al substrate; this method used sodium hypophosphite instead of formaldehyde as a reducing agent. The basic electroless solution consisted of $CuSO_4{\cdot}5H_2O$ as the main metal source, $NaH_2PO_2{\cdot}H_2O$ as the reducing agent, $C_6H_5Na_3O_7{\cdot}2H_2O$ and $NH_4Cl$ as the complex agents, and $NiSO_4{\cdot}6H_2O$ as the catalyser for the oxidation of the reducing agent, dissolved in deionized water. The pH of the Cu plating solutions was adjusted using $NH_4OH$. According to the variation of pH in the range of 6.5~8, the electroless plated Cu films were coated on screen printed Ag pattern/anodized Al/Al at $70^{\circ}C$. We investigated the surface morphology change of the Cu films using FE-SEM (Field Emission Scanning Electron Microscopy). The chemical composition of the Cu film was determined using XPS (X-ray Photoelectron Spectroscopy). The crystal structures of the Cu films were investigated using XRD (X-ray Diffraction). Using electroless plating at pH 7, the structures of the plated Cu-rich films were typical fcc-Cu; however, a slight Ni component was co-deposited. Finally, we found that the formation of Cu film plated selectively on PCB without any lithography is possible using a neutral electroless plating process.