• Bulletin of the Korean Chemical Society
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• 제24권5호
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• pp.647-649
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• 2003

• Bulletin of the Korean Chemical Society
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• 제30권4호
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• pp.853-856
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• 2009

Highly polycrystalline copper indium diselenide (CuInSe2, CIS) thin films were deposited on glass or ITO glass substrates by two-stage metal organic chemical vapor deposition (MOCVD) at relatively mild conditions, using Cuand In/Se-containing precursors. First, pure Cu thin film was prepared on glass or ITO glass substrates by using a single-source precursor, bis(ethylbutyrylacetate)copper(II) or bis(ethylisobutyrylacetato)copper(II). Second, on the resulting Cu films, tris(N,N-ethylbutyldiselenocarbamato)indium(III) was treated to produce CuInSe2 films by MOCVD method at 400 ${^{\circ}C}$. These precursors are very stable in ambient conditions. In our process, it was quite easy to obtain high quality CIS thin films with less impurities and uniform thickness. Also, it was found that it is easy to control the stoichiometric ratio of relevant elements on demands, leading to Cu or In rich CIS thin films. These CIS films were analyzed by XRD, SEM, EDX, and Near-IR spectroscopy. The optical band gap of the stoichiometric CIS films was about 1.06 eV, which is within an optimal range for harvesting solar radiation energy.

• 한국진공학회지
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• 제11권4호
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• pp.194-200
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• 2002

MOCVD(metal-organic chemical vapor deposition) Cu 박막을 여러 조건에서 열처리를 행하여 그 전기적 특성과 미세구조의 변화를 통해 적절한 열처리 조건을 찾고 그 효과를 조사하였다. Ar 1 torr, $400^{\circ}C$에서 열처리를 거친 Cu 박막의 비저항이 1.98 $\mu$Ω.cm로 가장 낮게 나타났으며, 결정성의 경우도 $I_{(111)}/I_{(200)}$의 비가 2.03에서 3.11로 열 처리를 거치지 않았을 경우와 비교해서 약 50% 정도 향상된 값을 나타내었다. 열처리 후의electromigration(EM) 테스트에서는 Ar 1 torr, $400^{\circ}C$에서 열처리를 거친 배선이 EM에 대한 가장 높은 저항성을 보였다. 이것은 열처리 후 낮은 비저항, (111) 결정면의 성장, 그리고 표면 거칠기의 감소에서 기인한 것이다.

• 한국진공학회:학술대회논문집
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• 한국진공학회 2012년도 제42회 동계 정기 학술대회 초록집
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• pp.377-377
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• 2012

Microprocessor technology now relies on copper for most of its electrical interconnections. Because of the high diffusivity of copper, Atomic layer deposition (ALD) $TaN_x$ is used as a diffusion barrier to prevent copper diffusion into the Si or $SiO_2$. Another problem with copper is that it has weak adhesion to most materials. Strong adhesion to copper is an essential characteristic for the new barrier layer because copper films prepared by electroplating peel off easily in the damascene process. Thus adhesion-enhancing layer of cobalt is placed between the $TaN_x$ and the copper. Because, cobalt has strong adhesion to the copper layer and possible seedless electro-plating of copper. Until now, metal film has generally been deposited by physical vapor deposition. However, one draw-back of this method is poor step coverage in applications of ultralarge-scale integration metallization technology. Metal organic chemical vapor deposition (MOCVD) is a good approach to address this problem. In addition, the MOCVD method has several advantages, such as conformal coverage, uniform deposition over large substrate areas and less substrate damage. For this reasons, cobalt films have been studied using MOCVD and various metal-organic precursors. In this study, we used $C_{12}H_{10}O_6(Co)_2$ (dicobalt hexacarbonyl tert-butylacetylene, CCTBA) as a cobalt precursor because of its high vapor pressure and volatility, a liquid state and its excellent thermal stability under normal conditions. Furthermore, the cobalt film was also deposited at various $H_2/NH_3$ gas ratio(1, 1:1,2,6,8) producing pure cobalt thin films with excellent conformality. Compared to MOCVD cobalt using $H_2$ gas as a reactant, the cobalt thin film deposited by MOCVD using $H_2$ with $NH_3$ showed a low roughness, a low resistivity, and a low carbon impurity. It was found that Co/$TaN_x$ film can achieve a low resistivity of $90{\mu}{\Omega}-cm$, a low root-mean-square roughness of 0.97 nm at a growth temperature of $150^{\circ}C$ and a low carbon impurity of 4~6% carbon concentration.

• 한국세라믹학회지
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• 제41권6호
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• pp.435-438
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• 2004

MOCVD is one of the major deposition techniques for Cu thin films and Ta-Si-N is one of promising barrier metal candidates for Cu with high thermal stability. Effects of hydrogen plasma pretreatment of the underlying Ta-Si-N film surface on the Cu nucleation in Cu MOCVD were investigated using scanning electron microscopy, X-ray photoelectron spectroscopy and Auger electron emission spectrometry analyses. Cu nucleation in MOCVD is enhanced as the rf-power and the plasma exposure time are increased in the hydrogen plasma pretreatment. The optimal plasma treatment process condition is the rf-power of 40 Wand the plasma exposure time of 2 min. The hydrogen gas flow rate in the hydrogen plasma pretreatment process does not affect Cu nucleation much. The mechanism through which Cu nucleation is enhanced by the hydrogen plasma pretreatment of the Ta-Si-N film surface is that the nitrogen and oxygen atoms at the Ta-Si-N film surface are effectively removed by the plasma treatment. Consequently the chemical composition was changed from Ta-Si-N(O) into Ta-Si at the Ta-Si-N film surface, which is favorable for Cu nucleation.

• 한국전기전자재료학회논문지
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• 제13권6호
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• pp.459-466
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• 2000

For the applications in the ultra-large-scale-integration (ULSI) metallization processing copper thin films have been prepared by metal organic chemical vapor deposition (MOCVD) technology on TiN/Si substrates. The films have been deposited with varying the experimental conditions of substrate temperatures and copper source vapor pressures. The films were then annealed in a vacuum condition after the deposition and the annealing effect to the electrical conductivity of the films was measured. The grain size and the crystallinity of the films were observed to be increased by the post annealing and the electrical conductivity was also increased. The best electrical property of the copper film was obtained by in-situ annealing treatment at above 40$0^{\circ}C$ for the sample prepared at 18$0^{\circ}C$ of the substrate temperature.

• 한국재료학회지
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• 제9권2호
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• pp.124-131
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• 1999

Copper film, which is expected to be used as interconnection material for 1 giga DRAM integrated circuits was deposited on hole and trench patterns by Metal Organic Chemical Vapor Deposition(MOCVD) method. After a reflow process, contact and L/S patterns were filled by copper and the characteristics of the Cu reflow process were investigated. When deposited Cu films were reflowed, grain growth and agglomeration of Cu have occurred in surfaces and inner parts of patterns as well as complete filling in patterns. Also Cu thin oxide layers were formed on the surface of Cu films reflowed in $O_2$ambient. Agglomeration and oxidation of Cu had bad influence on the electrical properties of Cu films especially, therefore, their removal and prevention were studied simultaneously. As a pattern size is decreased, preferential reflow takes place inside the patterns and this makes advantages in filling patterns of deep submicron size completely. With Cu reflow process, we could fill the patterns with the size of deep sub-micron and it is expected that Cu reflow process could meet the conditions of excellent interconnection for 1 giga DRAM device when it is combined with Cu MOCVD and CMP process.

• 한국표면공학회지
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• 제38권1호
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• pp.28-36
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• 2005

In this study, the reflow characteristics of copper thin films which is expected to be used as interconnection materials in the next generation semiconductor devices were investigated. Cu thin films were deposited on the TaN diffusion barrier by metal organic chemical vapor deposition (MOCVD) and annealed at the temperature between 250℃ and 550℃ in various ambient gases. When the Cu thin films were annealed in the hydrogen ambience compared with oxygen ambience, sheet resistance of Cu thin films decreased and the breakdown of TaN diffusion barrier was not occurred and a stable Cu/TaN/Si structure was formed at the annealing temperature of 450℃. In addition, reflow properties of Cu thin films could be enhanced in H₂ ambient. With Cu reflow process, we could fill the trench patterns of 0.16～0.24 11m with aspect ratio of 4.17～6.25 at the annealing temperature of 450℃ in hydrogen ambience. It is expected that Cu reflow process will be applied to fill the deep pattern with ultra fine structure in metallization.

• 한국산학기술학회논문지
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• 제1권1호
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• pp.37-42
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• 2000

유기금속 화학기상증착기술에 의해 폴리이미드 기판과 질화티탄 기판 위에 구리박막을 형성하였다. 구리박막을 화학기상증착기술에 의해 형성하면 종래의 물리적증착기술에 비하여 증착속도가 빠르고 층덮힘 성질이 좋아 산업체의 제품생산 응용에서 많은 장점이 있다. 이 장점은 제품의 생산성과 신뢰성에 영향을 미친다. 기판의 온도와 구리전구체 증기압력 조건을 변화시키며 반복실험을 실시하였으며, 시편에 따라서는 전기적 성질 향상을 위하여 후속 열처리를 수행하였다. 형성된 구리박막의 미세구조는 전자현미경으로 관찰하였으며, 전기비저항은 4점 프로브를 이용하여 측정하였다. 질화티탄을 기판으로 사용한 경우 구리박막에서는 섭씨 180도의 기판온도에서 만들어진 시편에서 가장 좋은 전기적 성질이 측정되었다. 한편, 폴리이미드 기판을 사용한 경우, 기상과 액상의 혼합상태 전구체를 이용하여 250 nm/min의 매우 높은 증착속도를 얻을 수 있었다.

• 마이크로전자및패키징학회지
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• 제6권1호
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• pp.31-37
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• 1999

본 연구에서는 집적회로의 배선공정에 적용될 무전해도금된 Cu박막의 열적 특성과 접착특성에 대하여 고찰하였다. 시편은 Si 기판에 MOCVD법으로 TaN 확산방지막을 증착시킨 후 그 위에 무전해도금법으로 Cu 막을 증착시켜 Cu/TaN/Si 구조의 다층박막을 제조하였다. 이렇게 제조된 Cu/TaN/Si 시편을 수소와 Ar 분위기에서 각각 열처리시킨 후 열처리온도에 따른 비저항을 측정함으로써 Cu박막의 열적 안정성을 분석하였다. Cu박막과 TaN확산방지막과의 접착특성을 분석하기 위하여 scratch test를 사용하였으며, TaN 확산방지막에 대한 무전해도금된 Cu배선막의 접착력은 일반적인 Thermal evaporation과 Sputturing 방법으로 증착된 Cu 박막의 경우와 비교함으로써 평가되었다. TaN 박막에 대한 Cu박막의 접착성을 평가하기 위해 scratch test를 행한 결과 무전해도금된 Cu박막의 경우 다른 방법으로 증착된 Cu 박막과 비슷한 접착특성을 나타내었으며, acoustic emission분석과 microscope 관찰 결과 sputtering이나 evaporation 방법으로 증착된 Cu박막 보다 무전해도금된 Cu박막이 상대 적으로 우수한 접착력을 나타내었다.