• Proceedings of the Korean Vacuum Society Conference
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• 2010.08a
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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.

• Journal of the Korean Ceramic Society
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• v.41 no.6
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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.

• Proceedings of the Korean Vacuum Society Conference
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• 2010.02a
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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.

• Korean Journal of Materials Research
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• v.11 no.5
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• pp.361-366
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• 2001

It is difficult to obtain high Cu nucleation density and continuous Cu films in Cu-MOCVD without cleaning the TiN substrate prior to Cu deposition. In this study effects of plasma precleaning on the Cu nucleation density were investigated using SEM, XPS, AES, AFM analyses. Direct plasma pretreatment is much more effective than remote plasma pretreatment in enhancing Cu nucleation. Cleaning effects are enhanced with increasing the rf-power and the plasma exposure time in hydrogen plasma pretreatment. The mechanism through which Cu nucleation is enhanced by plasma pretreatment is as follows: Hydrogen ion\ulcorner in the hydrogen plasma react with TiN to form Ti and $NH_3$ Cu nucleation is easier on the Ti substrate than TiN substrate.

• Progress in Superconductivity and Cryogenics
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• v.5 no.3
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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.

• Journal of the Institute of Electronics Engineers of Korea TE
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• v.39 no.1
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• pp.22-30
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• 2002

The nucleation of copper(Cu) with (hfac)iu(VTMS) oganometallic precursor is investigated for Si, $Sio_2$, TiN, $W_2N$ substrates. As the deposition temperature is increased, the dominant growth mechanism is observed to change from the nucleation of Cu particles to the clustering of Cu nuclei around $180^{\ciec}C$, independent of the employed substrates. It is also observed that the cleaning of substrate surfaces with the diluted HF solution improves the selectivity of Cu nucleation between TiN and $Sio_2$ substrates. Dimethyldichlorosilane treatment is found to passivate the surface of TiN substrate, contrary to the generally accepted belief, when the TiN substrate is cleaned by $H_2O_2$ solution before the treatment.

• Proceedings of the Materials Research Society of Korea Conference
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• 1993.11a
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• pp.87-88
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• 1993

• Korean Journal of Materials Research
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• v.11 no.9
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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.

• Journal of the Institute of Electronics Engineers of Korea SD
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• v.37 no.3
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• pp.27-33
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• 2000

The selective chemical vapor deposition techniques for Cu metallization were studied. For enhancing the selectivity, furnace annealing and N$_{2}$ plasma were treated on patterned TiN/BPSG prior to the copper deposition. As a result, Cu did not deposited lead to suppressing the nucleation on BPSG singificantly. With the increasement the plasma treatment temperature, copper nucleation on BPSG was suppressed mote effectively, From TOF-SIMS(Time-of-Flight Secondary ion Mass Spectrometry), it is considered that annealing and N$_{2}$ plasma treatment remove hydroxyl(0-H) group so that eliminating the nucleation site for copper precursor enhance the selectivity.

• Journal of Powder Materials
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• v.9 no.1
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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.