• The Korean Journal of Ceramics
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• v.4 no.3
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• pp.222-226
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• 1998

$Cu_3N$ film deposited on silicon oxide substrate by r.f. reactive sputtering technique. Synthesis and properties of copper nitride film were investigated for its possible application to Cu metallization as adhesive interlayer between copper and $SiO_2. Cu_3N$ film was synthesized at the substrate temperature ranging from $100^{\circ}C$ to $200^{\circ}C$ and at nitrogen gas ratio above $X_{N2}=0.4. Cu_3N, CuN_x$, and FGM-structured $Cu/CuN_x$ films prepared in this work passed Scotch-tape test and showed improved adhesion property to silicon oxide substrate compared with Cu film. Electrical resistivity of copper nitride film had a dependency on its lattice constant and was ranged from 10-7 to 10-1 $\Omega$cm. Copper nitride film was, however, unstable when it was annealed at the temperature above $400^{\circ}C$.

• 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 Materials Research Society of Korea Conference
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• 1995.11a
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• pp.41-41
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• 1995

• 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.

• Journal of the Korean Institute of Electrical and Electronic Material Engineers
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• v.17 no.3
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• pp.272-277
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• 2004

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.

• Journal of the Korean Crystal Growth and Crystal Technology
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• v.6 no.3
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• pp.318-326
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• 1996

This study is to investigate a chemical vapor deposition technique of copper film which is expected to be more useful as metallizations of microcircuit fabrication. An experimental equipment was designed and set-up for this study, and a Cu-precursor used that is a metal-organic compound, named (hfac)Cu(I)VTMS ; (hevaflouoroacetylacetonate trimethyvinylsilane copper). Base pressure of the experimental system is in $10^{-6}$ Torr, and the chamber pressure and the substrate temperature can be controlled in the system. Before the deposition of copper thin film, tungsten or titanium nitride film was deposited onto the silicon wafer. Helium has been used as carrier gas to control the deposition rate. As a result, deposition rate was measured as $1,800\;{\AA}/min$ at $220^{\circ}C$ which is higher than the results of previous studies, and the average surface roughness was measured as about $200\;{\AA}$. A deposition selectivity was observed between W or TiN and $SiO_{2}$ substrates below $250^{\circ}C$, and optimum results are observed at $180^{\circ}C$ of substrate temperature and 0.8 Torr of chamber pressure.

• 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.

• Korean Journal of Materials Research
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• v.13 no.3
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• pp.174-179
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• 2003

Thin copper films were grown by electrodeposition on copper seed layers which were grown by sputtering of an ultra-pure copper target on tantalum nitride-coated silicon wafers and subsequently, cleaned in ECR plasma. The copper films were then subjected to ⅰ) vacuum annealing, ⅱ) rapid thermal annealing (RTA) and ⅲ) rapid thermal nitriding (RTN) at various temperatures over different periods of time. XRD, SEM, AFM and resistivity measurements were done to ascertain the optimum heat treatment condition for obtaining film with minimum resistivity, predominantly (111)-oriented and smoother surface morphology. The as-deposited film has a resistivity of ∼6.3 $\mu$$\Omega$-cm and a relatively small intensity ratio of (111) and (200) peaks. With heat treatment, the resistivity decreases and the (111) peak becomes dominant, along with improved smoothness of the copper film. The optimum condition (with a resistivity of 1.98 $\mu$$\Omega$-cm) is suggested as the rapid thermal nitriding at 400oC for 120 sec.

• 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.

• 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.