• 한국진공학회:학술대회논문집
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• 한국진공학회 2010년도 제39회 하계학술대회 초록집
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• pp.246-246
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• 2010

As the trench width in the interconnect technology decreases down to nano-scale below 50 nm, superconformal gap-filling process of Cu becomes very critical for Cu interconnect. Obtaining superconfomral gap-filling of Cu in the nano-scale trench or via hole using MOCVD is essential to control nucleation and growth of Cu. Therefore, nucleation of Cu must be suppressed near the entrance surface of the trench while Cu layer nucleates and grows at the bottom of the trench. In this study, suppression of Cu nucleation was achieved by treating the Ru barrier metal surface with capacitively coupled hydrogen plasma. Effect of hydrogen plasma pretreatment on Cu nucleation was investigated during MOCVD on atomic-layer deposited (ALD)-Ru barrier surface. It was found that the nucleation and growth of Cu was affected by hydrogen plasma treatment condition. In particular, as the plasma pretreatment time and electrode power increased, Cu nucleation was inhibited. Experimental data suggests that hydrogen atoms from the plasma was implanted onto the Ru surface, which resulted in suppression of Cu nucleation owing to prevention of adsorption of Cu precursor molecules. Due to the hydrogen plasma treatment of the trench on Ru barrier surface, the suppression of Cu nucleation near the entrance of the trenches was achieved and then led to the superconformal gap filling of the nano-scale trenches. In the case for without hydrogen plasma treatments, however, over-grown Cu covered the whole entrance of nano-scale trenches. Detailed mechanism of nucleation suppression and resulting in nano-scale superconformal gap-filling of Cu will be discussed in detail.

• 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.

• 한국진공학회:학술대회논문집
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• 한국진공학회 2009년도 제38회 동계학술대회 초록집
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• pp.249-249
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• 2010

The effect of forming a passivation layer was investigated in superconformal Cu gap-filling of the nano-scale trench with atomic-layer deposited (ALD)-Ru glue layer. It was discovered that the nucleation and growth of Cu during metal-organic chemical vapor deposition (MOCVD) were affected by hydrogen plasma treatments. Specifically, as the plasma pretreatment time increased, Cu nucleation was suppressed proportionally. XPS and Thermal Desorption Spectroscopy indicated that hydrogen atoms passivate the Ru surface, which leads to suppression of Cu nucleation owing to prevention of adsorption of Cu precursor molecules. For gap-fill property, sub 60-nm ALD Ru trenches without the plasma pretreatment was blocked by overgrown Cu after the Cu deposition. With the plasma pretreatment, superconformal gap filling of the nano-scale trenches was achieved due to the suppression of Cu nucleation near the entrances of the trenches. Even the plasma pretreatment with bottom bias leads to the superconformal gap-filling.

• 한국재료학회지
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• 제11권5호
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• pp.361-366
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• 2001

TiN barrier 막 위에 metal organic chemical vapor deposition (MOCVD)법으로 Cu막을 증착함에 있어 TiN막 표면을 먼저 세정처리하지 않고 바로 Cu막을 증착하려하면 Cu의 핵생성이 어렵고, 그 결과 연속된 Cu막이 형성되지 못한다. 본 연구에서는 SEM, AES, AFM 등의 분석방법을 사용하여 TiN 막 표면에 대한 플라즈마 전처리 세정이 Cu막의 핵생성에 미치는 효과에 관하여 조사하였다. Gu의 전처리 세정방법으로는 direct플라즈마 방식이 원거리 플라즈마 방식보다 훨씬 더 효과적이다. 또한 수소플라즈마 전처리 시 rf-power와 플라즈마 조사시간이 증가함에 따라 세정효과는 더 증대된다. 플라즈마 전처리가 Cu의 핵생성을 고양시키는 원리는 다음과 같다. 플라즈마 내의 수소이온이 TiN과 반응하여 $NH_3$가 됨으로서 질소 성분이 제거되어 TiN이 Ti로 환원된다. Cu는 TiN기판보다는 Ti기판상에서 핵생성이 더 잘 되므로 플라즈마 전처리는 Cu의 핵생성을 돕는 효과를 가져온다.

• 한국초전도ㆍ저온공학회논문지
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• 제5권3호
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• pp.1-5
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• 2003

The effect of CeO$_2$ coating on the surface nucleation of the top-seeded melt-growth processed YBCO superconductors was studied. It was effective that the coating of Y123 compact surfaces by CeO$_2$ powder suppressed the undesirable subsidiary YBa$_2$Cu$_3$O$_{7-y}$ (Y123) nucleation during melt processing. BaCeO$_3$ was formed in the CeO$_2$-coated layers, which might cause a CuO-excessive liquid at the partial melt stage of $Y_2$BaCuO$_{5}$(Y211) plus liquid, and thus the Y123 nucleation at the YBCO compact surfaces could be suppressed during the melt growth of Y123 grain. In addition, the CeO$_2$ refined the Y211 particles near the compact / coating interface. While the levitation forces of the top surfaces with and without CeO$_2$ coating were similar to each other, the levitation force of the interior of the CeO$_2$ coated sample was higher than that of the interior of the sample without CeO$_2$ coating, which was attributed to the suppression of subsidiary Y123 nucleation at the compact walls.s.s.

• 대한전자공학회논문지TE
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• 제39권1호
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• pp.22-30
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• 2002

Si, SiO/sup 2/, TiN, W/sup 2/N 기판 위에 (hfac)Cu(VTMS) 유기금속 전구체로 증착된 구리 핵을 조사하였다. 증착온도가 증가함에 따라, 기판 종류에 상관없이 180。C에서 구리 핵이 클러스터링으로 성장하는 메커니즘을 관찰하였다. 또한, HF용액으로 세척한 TiN 과 SiO/sup 2/가 공존하는 기판에서 구리 핵의 선택성이 향상됨을 관찰하였다. TiN을 H/sup 2/O/sup 2/로 세척한 후 Dimethyldichlorosilane 처리했을 때 표면이 passivation됨을 확인하였다.

• 한국재료학회:학술대회논문집
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• 한국재료학회 1993년도 추계 학술발표 강연 및 논문 개요집
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• pp.87-88
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• 1993

• 한국재료학회지
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• 제11권9호
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• pp.802-809
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• 2001

Electroplating is an attractive alternative deposition method for copper with the need for a conformal and conductive seed layer In addition, the Cu seed layer should be highly pure so as not to compromise the effective resistivity of the filled copper interconnect structure. This seed layer requires low electrical resistivity, low levels of impurities, smooth interface, good adhesion to the barrier metal and low thickness concurrent with coherence for ensuring void-free fill. The electrical conductivity of the surface plays an important role in formation of initial Cu nuclei, Cu nucleation is much easier on the substrate with higher electrical conductivities. It is also known that the nucleation processes of Cu are very sensitive to surface condition. In this study, copper seed layers deposited by magnetron sputtering onto a tantalum nitride barrier layer were used for electroplating copper in the forward pulsed mode. Prior to electroplating a copper film, the Cu seed layer was cleaned by plasma H$_2$ and $N_2$. In the plasma treatment exposure tome was varied from 1 to 20 min and plasma power from 20 to 140W. Effects of plasma pretreatment to Cu seed/Tantalum nitride (TaN)/borophosphosilicate glass (BPSG) samples on electroplating of copper (Cu) films were investigated.

• 대한전자공학회논문지SD
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• 제37권3호
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• pp.27-33
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• 2000

선택성을 향상시키기 위해서 BPSG(Borophosphosilicate glass) 위에 형성한 TiN 패턴을 로(furnace) 열처리와 질소 플라즈마 처리를 한 후 유기 화학 기상 증착법(MOCVD； Metal Organic Chemical Vapor Deposition)으로 구리 박막을 증착하였다. 먼저 650℃∼750℃에서 열처리한 후 150℃에서 구리 박막을 증착시켰을 때 750℃에서 열처리한 경우 TiN 표면 위에만 선택적으로 구리 증착이 일어났다. 질소 플라즈마 처리를 한 경우도 마찬가지로 BPSG 위에 구리 핵 형성이 억제됨을 알 수 있었다. 플라즈마 처리 온도를 증가시킬수록 BPSG 위의 구리 핵 형성이 더 효과적으로 억제되었다. 열처리와 플라즈마 처리 후 증착된 기판 표면을 TOF-SIMS(Time-of-Flight Secondary Ion Mass Spectrometry)로 분석하였을 때 플라즈마 처리가 BPSG 표면의 구리 증착 작용기인 0-H(hydroxyl)기를 제거하여 구리의 선택성이 향상되었다고 해석하였다.

• 한국분말재료학회지
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• 제9권1호
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• pp.19-24
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• 2002

This paper reports the results of an investigation into the effect of Cu additions upon the nano-crystallization behaviour of an Al-Y-Ni alloy. 1 at.% Cu was added to a base alloy of Al/sub 88/Y₄Ni/sub 8/ either by substitution for Al to form Al/sub 87/Y₄Ni/sub 8/Cu₁, or by substitution for Ni to form Al/sub 88/Y₄Ni/sub 7/Cu₁. Consistent with previous findings in the literature, the substitution of Cu for Al was found to increase the thermal stability of the amorphous phase whereas the substitution of Cu for Ni was found to decrease its thermal stability. Comparing the microstructures of these alloys after heat treatment to produce equivalent volume fractions of Al nanocrystals showed average grain sizes of 14 nm, 12 nm and 9 nm for the alloys Al/sub 88/Y₄Ni/sub 8/, Al/sub 87/Y₄Ni/sub 8/Cu₁respectively. The effect of Cu in refining the size of the nanocrystals was attributed to enhanced nucleation increasing the number density of the nanocrystals, rather than diffusion limited or interface limited growth.