• 한국전기전자재료학회:학술대회논문집
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• 한국전기전자재료학회 2004년도 추계학술대회 논문집 Vol.17
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• pp.132-135
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• 2004

현재 사용 되고 있는 Cu CMP slurry에서 pH 적정제의 역할은 slurry의 연마 거동을 결정 하는 중요한 요소이다. 일반적으로 사용 되고 있는 적정제로는 $NH_4OH$, KOH가 있다. 구리 CMP용 슬러리내에서 CMP 공정 중에 과산화수소 $(H_2O_2)$의 영향에 관한 연구는 있으나, 과산화수소의 농도 (vol %) 변화에 따라서 pH적정제가 하는 역할과 반응이 CMP 공정중에 미치는 영향에 관해서 연구된 바 없다. 이 논문에서는 pH 적정제가 과산화수소의 농도에 따라서 산성, 중성, 염기성에서 어떠한 변화를 일으키는지에 관해서 dynamic etch rate과 removal rate을 비교 하였고, static etch rate을 이용하여 Cu 표면이 etching 되는 속도를 비교 하였다. 그 결과, 산성과 중성에서는 $NH_4OH$와 KOH의 경향성은 비슷하였으나, 염기성에서는 KOH를 첨가한 경우 변화가 나타나지 않았다. 따라서, pH가 염기성으로 갈수록 과산화수소의 저 농도에서 $NH_4OH$의 영향이 더 커짐을 알 수 있었다.

• 한국재료학회:학술대회논문집
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• 한국재료학회 2001년도 춘계학술발표강연 및 논문개요집
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• pp.80-80
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• 2001

• 한국세라믹학회:학술대회논문집
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• 한국세라믹학회 2002년도 추계총회 및 연구발표회 초록집
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• pp.132-132
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• 2002

• 한국재료학회:학술대회논문집
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• 한국재료학회 2005년도 춘계학술발표대회 및 제8회 신소재 심포지엄 논문개요집
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• pp.251-251
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• 2005

• 한국전기전자재료학회:학술대회논문집
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• 한국전기전자재료학회 2008년도 하계학술대회 논문집 Vol.9
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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.

• 한국전기전자재료학회:학술대회논문집
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• 한국전기전자재료학회 2003년도 하계학술대회 논문집 Vol.4 No.1
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• pp.382-385
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• 2003

Chemical mechanical polishing(CMP) is an essential process in the production of copper-based chips. On this work, the stability of Hydrogen Peroxide($H_2O_2$) as oxidizer of Cu CMP slurry has been investigated. $H_2O_2$ is known as the most common oxidizer in Cu CMP slurry. Copper slowly dissolves in $H_2O_2$ solutions and the interaction of $H_2O_2$ with copper surface had been studied in the literature. Because hydrogen peroxide is a weak acid in aqueous solutions, a passivation-type slurry chemistry could be achieved only with pH buffered solution.[1] Moreover, $H_2O_2$ is so unstable that its stabilization is needed using as oxidizer. As adding KOH as pH buffering agent, stability of $H_2O_2$ decreased. However, stability went up with putting in small amount of BTA as film forming agent. There was no difference of $H_2O_2$ stability between KOH and TMAH at same pH. On the other hand, $H_2O_2$ dispersion of TMAH is lower than that of KOH. Furthermore, adding $H_2O_2$ in slurry in advance of bead milling lead to better stability than adding after bead milling. Generally, various solutions of phosphoric acids result in a higher stability. Using Alumina C as abrasive was good at stabilizing for $H_2O_2$; moreover, better stability was gotten by adding $H_3PO_4$.

• Transactions on Electrical and Electronic Materials
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• 제4권2호
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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.

• 한국전기전자재료학회:학술대회논문집
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• 한국전기전자재료학회 2003년도 춘계학술대회 논문집 센서 박막재료 반도체 세라믹
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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).

• 한국마이크로전자및패키징학회:학술대회논문집
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• 한국마이크로전자및패키징학회 2001년도 추계 기술심포지움
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• pp.230-234
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• 2001

본 연구에서는 Alumina(A1$_2$O$_3$) based Slurry를 이용하여 CU CMP를 할 때 첨가제의 영향을 Removal rate와 Etch rate 측면에서 조사하였다. 각각의 첨가제의 종류와 조성의 변화에 따라 Polishing에 미치는 영향을 연구하였다. Cu의 Removal rate는 Etch rate와 달리 Organic acid의 종류에 직접적으로 영향을 받는다. Citric acid는 높은 Removal rate와 슬러리 내에서 안정성이 가장 좋은 결과를 보이고 있다. Citric acid의 농도가 증가하면 증가할수록 Removal rate는 증가하였다. BTA의 농도에 따라서 Cu의 Removal rate와 Etch rate의 감소를 확인할 수 있다. EDTA의 농도에 따라서는 증가함을 볼 수 있다.

• 한국전기전자재료학회:학술대회논문집
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• 한국전기전자재료학회 2004년도 하계학술대회 논문집 Vol.5 No.1
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• pp.227-230
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• 2004

As the organic acids were added in the slurry, zeta potential of alumina was changed to negative value and IEP value was shifted from alkaline to acidic pH. In citric acid based slurry, Cu surface continuously dissolved and etching depth linearly increased. On the contrary, passivation layer was grown on Cu surface in oxalic acid based slurry. As the platen rotation speed increased, Preston coefficient decreased in both slurries. With oxalic acid based slurry, at low velocity, removal rate is high value because of high friction force compared to citric acid based slurry. As platen velocity increased, removal of Cu in citric acid based slurry became higher value than oxalic acid based slurry. Typical lubrication behaviors were observed in both slurries. As Sommerfeld number increased, COF values gradually decreased and then re-increased. It indicated that lubrication was changed to direct contact or semi-direct contact mode to hydro-lubrication mode.