• 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.

• 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.

• 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.

• 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.

• Journal of Sensor Science and Technology
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• v.13 no.3
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• pp.195-198
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• 2004

For a diffusion barrier against copper, tantalum nitride films have been deposited on $SiO_{2}$ by atomic layer deposition (ALD), using PEMAT(Pentakis(ethylmethylamino)tantalum) and $NH_{3}$ as precursors, Ar as purging gas. The deposition rate of TaN at substrate temperature $250^{\circ}C$ was about $0.67{\AA}$ per one cycle. The stability of TaN films as a Cu diffsion barrier was tested by thermal annealing for 30 minutes in $N_{2}$ ambient and characterized through XRD, sheet resistance, and C-V measurement(Cu($1000{\AA}$)/TaN($50{\AA}$)/$SiO_{2}$($2000{\AA}$)/Si capacitor fabricated), which prove the TaN film maintains the barrier properties Cu below $400^{\circ}C$.

• 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.

• 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.

• Proceedings of the Korean Vacuum Society Conference
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• 2010.08a
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• pp.178-178
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• 2010

With the scaling down of ULSI(Ultra Large Scale Integration) circuit of CMOS(Complementary Metal Oxide Semiconductor)based electronic devices, the electronic devices become more faster and smaller size that are promising field of semiconductor market. However, very narrow line width has some disadvantages. For example, because of narrow line width, deposition of conformal and thin barrier is difficult. Besides, proportion of barrier width is large, thus resistance is high. Conventional PVD(Physical Vapor Deposition) thin films are not able to gain a good quality and conformal layer. Hence, in order to get over these side effects, deposition of thin layer used of ALD(Atomic Layer Deposition) is important factor. Furthermore, it is essential that copper atomic diffusion into dielectric layer such as silicon oxide and hafnium oxide. If copper line is not surrounded by diffusion barrier, it cause the leakage current and devices degradation. There are some possible methods for improving the these secondary effects. In this study, TaNx, is used of Tertiarybutylimido tris (ethylamethlamino) tantalum (TBITEMAT), was deposited on the 24nm sized trench silicon oxide/silicon bi-layer substrate with good step coverage and high quality film using plasma enhanced atomic layer deposition (PEALD). And then copper was deposited on TaNx barrier using same deposition method. The thickness of TaNx was 4~5 nm. TaNx film was deposited the condition of under $300^{\circ}C$ and copper deposition temperature was under $120^{\circ}C$, and feeding time of TaNx and copper were 5 seconds and 5 seconds, relatively. Purge time of TaNx and copper films were 10 seconds and 6 seconds, relatively. XRD, TEM, AFM, I-V measurement(for testing leakage current and stability) were used to analyze this work. With this work, thin barrier layer(4~5nm) with deposited PEALD has good step coverage and good thermal stability. So the barrier properties of PEALD TaNx film are desirable for copper interconnection.

• Journal of Powder Materials
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• v.10 no.3
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• pp.164-167
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• 2003

The mechanical alloying effect has been studied on the three Cu-based alloy systems with a positive heat of mixing. The extended bcc solid solution has been formed in the Cu-V system and an amorphous phase in the Cu-Ta system. However, it is round that a mixture of nanocrystalline Cu and Mo Is formed in the Cu-Mo system. The neutron diffraction has been employed at a main tool to characterize the detailed amorphization process. The formation of an amorphous phase in Cu-Ta system can be understood by assuming that the smaller Cu atoms preferentially enter into the bcc Ta lattice during ball milling.