• Korean Journal of Materials Research
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• v.15 no.6
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• pp.426-430
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• 2005

Chemical mechanical polishing (CMP) is an essential process in the production of integrated circuits containing copper interconnects. The effect of alanine in reactive slurries representative of those that might be used in copper CMP was studied with the aim of improving selectivity between copper(Cu) film and tantalum-nitride(TaN) film. We investigated the pH effect of nano-colloidal silica slurry containing alanine through the chemical mechanical polishing test for the 8(inch) blanket wafers as deposited Cu and TaN film, respectively. The copper and tantalum-nitride removal rate decreased with the increase of pH and reaches the neutral at pH 7, then, with the further increase of pH to alkaline, the removal rate rise to increase soddenly. It was found that alkaline slurry has a higher removal rate than acidic and neutral slurries for copper film, but the removal rate of tantalum-nitride does not change much. These tests indicated that alanine may improve the CMP process by controlling the selectivity between Cu and TaN film.

• Proceedings of the Korean Institute of Electrical and Electronic Material Engineers Conference
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• 2009.06a
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• pp.57-57
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• 2009

반도체 device가 고집적화 및 다층화 되어짐에 따라 현재 사용되고 있는 구리 interconnect의 확산방지막인 Ta/TaN은 많은 문제가 발생하고 있다. 고집적화 된 반도체 소자에 적용시키기에는 Ta/TaN 확산 방지막의 고유 저항값이 매우 크고, 구리의 증착에 필요한 seed layer의 크기도 문제화 된다고 보고되어지고 있다. 이러한 이유로 인해 점차 고집적화 되어지는 반도체 기술에 맞추어 새로운 확산 방지막에 대한 연구가 현재 활발히 이루어지고 있다. 이에 새로운 확산 방지막으로써 대두되고 연구되고 있는 재료가 Ruthenium (Ru)이다. Ru은 공기 중에서 매우 안정하고 고유저항 값 또한 $13\;{\mu}{\Omega}\;cm$의 Ta에 비해 $7.1\;{\mu}{\Omega}\;cm$의 매우 작은 고유저항 특성을 가지고 있다. 또한, Ru은 구리와의 우수한 접착성으로 인해 구리의 interconnect의 형성에 있어 seed layer가 필요하지 않을 뿐만 아니라 높은 annealing 온도에서도 무시할 만큼 작은 solid solubility를 가지며 구리와의 계면에서 새로운 화합물을 형성하지 않으며 annealing시 구리의 delamination을 유발시키지도 않는다. 이에 따라, 평탄화와 소자 분리를 위하여 chemical mechanical planarization (CMP) 공정이 필요하게 되었다. 하지만, Ru의 noble한 성질과 Ru 확산방지막 CMP공정 시 노출되는 다른 이종 물질 사이의 최적화 된 selectivity를 구현하는데 많은 어려움이 있다. 이로인해 Ru 확산 방지막을 위한 CMP slurry에 대한 연구는 아직 미흡한 수준이다. 본 연구에서는 Ru이 확산방지막으로 사용되었을 때 이를 위한 CMP slurry에 대한 평가와 연구가 이루어졌다. Slurry 조성과 농도 및 pH에 따른 전기 화학적 분석을 통하여 slurry 내에서 각각의 막질들이 어떠한 상태로 존재하는지 분석해 보았다. 또한, Ru을 비롯한 이종막질들의 etch rate, removal rate와 selectivity에 대한 연구가 진행되었다. 최종적으로 Ru 확산방지막 CMP를 위한 최적화된 slurry를 제안하였다.

• Proceedings of the Materials Research Society of Korea Conference
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• 2005.05a
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• pp.47-47
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• 2005

• Proceedings of the Materials Research Society of Korea Conference
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• 2005.05a
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• pp.49-49
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• 2005

• Proceedings of the Korean Institute of Electrical and Electronic Material Engineers Conference
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• 2003.05c
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• pp.162-165
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• 2003

The corrosion characteristics of diffusion barrier in Copper CMP has been investigated. Key experimental variables that has been investigated are the corrosion rate by different agents containing slurry of Cu CMP. Whenever Cu and Ta films were corroded adding each oxidizer, the corrosion rate of Ta was much lower than that of Cu. That is, the difference in the corrosion rates of Ta by oxidizer was not larger as compared with Cu. As corroded by complexing agents, the corrosion rate of Ta was close to O. The corrosion rate of Ta increased as added $HNO_3$ and $CH_3COOH$ compared with the reference slurry; on the other hand, it decreased with addition of HF. In addition, resulting corrosion rate went up with lower pH of agent. The corrosion rates by agents were however significant small; hence, it doesn't affect on the removal rate of Cu CMP practically. Consequently, this can be explained by assuming that the mechanical effect dominates than the chemical effect on the polishing rate of Ta(TaN).

• Proceedings of the Korean Institute of Electrical and Electronic Material Engineers Conference
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• 2004.04b
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• pp.38-41
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• 2004

The oxidizer plays an important role in the metal chemical mechanical polishing(CMP) slurry. Currently, the oxidizer used in CMP slurry is nearly divided into several kinds such as $Fe(NO_3)_3$, $H_2O_2$, $KIO_3$, and $H_5IO_6$. It is generally known that oxidizer character of $H_2O_2$ is more effective than other oxidizers. In this work, we have been studied the characteristics for the $H_2O_2$ concentration of copper slurry, which can applicable in the recent semiconductor manufacturing process. Also, it plays an important role in the planarization of copper films using copper slurries during micro-electronic device fabrication. In this work, we confirmed that removal rate of Cu/TaN changed by $H_2O_2$ concentration on copper slurry. And we used $KMnO_4$ in the measurement method of $H_2O_2$. In analysis results, we confirmed that the difference of results is large. We thought that the difference was due to organic component existence. So in titration method of $H_2O_2$ concentration, we used $Na_2S_2O_3$ instead of $KMnO_4$ as solution. Consequently, using the titration method, we could calculate correct data reduced error. And $H_2O_2$ concentration has been adjusted to the target concentration of 0.1 wt%.

• Proceedings of the Korean Institute of Electrical and Electronic Material Engineers Conference
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• 2008.06a
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• pp.546-546
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• 2008

Copper (Cu) Chemical mechanical polishing (CMP) has been an essential process for Cu wifing of DRAM and NAND flash memory beyond 45nm. Copper has been employed as ideal material for interconnect and metal line due to the low resistivity and high resistant to electro-migration. Damascene process is currently used in conjunction with CMP in the fabrication of multi-level copper interconnects for advanced logic and memory devices. Cu CMP involves removal of material by the combination of chemical and mechanical action. Chemicals in slurry aid in material removal by modifying the surface film while abrasion between the particles, pad, and the modified film facilitates mechanical removal. In our research, we emphasized on the role of chemical effect of slurry on Cu CMP, especially on the effect of amine functional group on removal rate selectivity between Cu and Tantalum-nitride (TaN) film. We investigated the two different kinds of complexing agent both with amine functional group. On the one hand, Polyacrylamide as a polymer affected the stability of abrasive, viscosity of slurry and the corrosion current of copper film especially at high concentration. At higher concentration, the aggregation of abrasive particles was suppressed by the steric effect of PAM, thus showed higher fraction of small particle distribution. It also showed a fluctuation behavior of the viscosity of slurry at high shear rate due to transformation of polymer chain. Also, because of forming thick passivation layer on the surface of Cu film, the diffusion of oxidant to the Cu surface was inhibited; therefore, the corrosion current with 0.7wt% PAM was smaller than that without PAM. the polishing rate of Cu film slightly increased up to 0.3wt%, then decreased with increasing of PAM concentration. On the contrary, the polishing rate of TaN film was strongly suppressed and saturated with increasing of PAM concentration at 0.3wt%. We also studied the electrostatic interaction between abrasive particle and Cu/TaN film with different PAM concentration. On the other hand, amino-methyl-propanol (AMP) as a single molecule does not affect the stability, rheological and corrosion behavior of the slurry as the polymer PAM. The polishing behavior of TaN film and selectivity with AMP appeared the similar trend to the slurry with PAM. The polishing behavior of Cu film with AMP, however, was quite different with that of PAM. We assume this difference was originated from different compactness of surface passivation layer on the Cu film under the same concentration due to the different molecular weight of PAM and AMP.

• Transactions on Electrical and Electronic Materials
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• v.4 no.2
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• pp.1-4
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• 2003

The purpose of this study was to investigate the characteristics of slurry including phosphoric acid for chemical-mechanical planarization of copper and tantalum nitride. In general, the slurry for copper CMP consists of alumina or colloidal silica as an abrasive, organic acid as a complexing agent, an oxidizing agent, a film forming agent, a pH control agent and additives. Hydrogen peroxide (H$_2$O$_2$) is the material that is used as an oxidizing agent in copper CMP. But, the hydrogen peroxide needs some stabilizers to prevent decomposition. We evaluated phosphoric acid (H$_3$PO$_4$) as a stabilizer of the hydrogen peroxide as well as an accelerator of the tantalum nitride CMP process. We also estimated dispersion stability and zeta potential of the abrasive with the contents of phosphoric acid. An acceleration of the tantalum nitride CMP was verified through the electrochemical test. This approach may be useful for the development of the 2$\^$nd/ step copper CMP slurry and hydrogen peroxide stability.

• Proceedings of the Korean Institute of Electrical and Electronic Material Engineers Conference
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• 2003.05c
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• pp.158-161
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• 2003

The primary aim of this study is to investigate new semi-abrasive free slurry including acid colloidal silica and hydrogen peroxide for copper chemical-mechanical planarization (CMP). In general, slurry for copper CMP consists of colloidal silica as an abrasive, organic acid as a complex-forming agent, hydrogen peroxide as an oxidizing agent, a film forming agent, a pH control agent and several additives. We developed new semi-abrasive free slurry (SAFS) including below 0.5% acid colloidal silica. We evaluated additives as stabilizers for hydrogen peroxide as well as accelerators in tantalum nitride CMP process. We also estimated dispersion stability and Zeta potential of the acid colloidal silica with additives. The extent of enhancement in tantalum nitride CMP was verified through anelectrochemical test. This approach may be useful for the application of single and first step copper CMP slurry with one package system.

• Transactions on Electrical and Electronic Materials
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• v.5 no.6
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• pp.233-236
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• 2004

Copper metallization has been used in high-speed logic ULSI devices instead of the conventional aluminum alloy metallization. One of the key issues in copper CMP is the development of slurries that can provide high removal rates. In this study, the effects of slurry chemicals and pH for slurry dispersion stability on Cu CMP process characteristics have been performed. The experiments of copper slurries containing each different alumina and colloidal silica particles were evaluated for their selectivity of copper to TaN and $SiO_{2}$ films. Furthermore, the stability of copper slurries and pH are important parameters in many industries due to problems that can arise as a result of particle settling. So, it was also observed about several variables with various pH.