• Proceedings of the Korean Vacuum Society Conference
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• 2013.08a
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• pp.78-78
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• 2013

Recently, many platinoid metals like platinum and ruthenium have been used as an electrode of microelectronic devices because of their low resistivity and high work-function. However the material cost of Ru is very expensive and it usually takes long initial nucleation time on SiO2 during chemical deposition. Therefore many researchers have focused on how to enhance the initial growth rate on SiO2 surface. There are two methods to deposit Ru film with atomic layer deposition (ALD); the one is thermal ALD using dilute oxygen gas as a reactant, and the other is plasma enhanced ALD (PEALD) using NH3 plasma as a reactant. Generally, the film roughness of Ru film deposited by PEALD is smoother than that deposited by thermal ALD. However, the plasma is not favorable in the application of high aspect ratio structure. In this study, we used a bis(ethylcyclopentadienyl)ruthenium [Ru(EtCp)2] as a metal organic precursor for both thermal and plasma enhanced ALDs. In order to reduce initial nucleation time, we use several methods such as Ar plasma pre-treatment for PEALD and usage of sacrificial RuO2 under layer for thermal ALD. In case of PEALD, some of surface hydroxyls were removed from SiO2 substrate during the Ar plasma treatment. And relatively high surface nitrogen concentration after first NH3 plasma exposure step in ALD process was observed with in-situ Auger electron spectroscopy (AES). This means that surface amine filled the hydroxyl removed sites by the NH3 plasma. Surface amine played a role as a reduction site but not a nucleation site. Therefore, the precursor reduction was enhanced but the adhesion property was degraded. In case of thermal ALD, a Ru film was deposited from Ru precursors on the surface of RuO2 and the RuO2 film was reduced from RuO2/SiO2 interface to Ru during the deposition. The reduction process was controlled by oxygen partial pressure in ambient. Under high oxygen partial pressure, RuO2 was deposited on RuO2/SiO2, and under medium oxygen partial pressure, RuO2 was partially reduced and oxygen concentration in RuO2 film was decreased. Under low oxygen partial pressure, finally RuO2 was disappeared and about 3% of oxygen was remained. Usually rough surface was observed with longer initial nucleation time. However, the Ru deposited with reduction of RuO2 exhibits smooth surface and was deposited quickly because the sacrificial RuO2 has no initial nucleation time on SiO2 and played a role as a buffer layer between Ru and SiO2.

• Korean Journal of Materials Research
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• v.9 no.3
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• pp.244-250
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• 1999

MOCVD TiN films were prepared from a new TiN precursor, tetrakis(etylmethylamino)titanium (TEMAT) and ammonia. Deposition of TiN films from a single precursor, TEMA T yielded the growth rates of $70 to 1050\AA$/min, depending on the deposition temperature. Furthermore, the excellent bottom coverage of -90% over $0.35\mu\textrm{m}$ contacts was obtained at $275^{\circ}C$. The addition of ammonia to TEMA T lowered the resistivity of as- deposited TiN film to ~ $800\mu\omega-cm$ from $3500~6000\mu\omega-cm$ and improved the stability of TiN film in air. Examination of the films by Auger electron spectroscopy(AES) showed that the oxygen and carbon contents decreased with the addition of ammonia. However, increasing ammonia flow rate decreased the bottom coverage of TiN films over $0.5\mu\textrm{m}$ contacts, probably due to the high sticking coefficient of intermediate species produced from the gas phase reaction of TEMA T and ammonia. Based on the byproduct gases detected by the quadrupole mass spectrometer (QMS), the transammination reaction was proposed to be responsible for TiN deposition. In addition, XPS analysis revealed that the carbon in the films made from TEMA T and ammonia was metallic carbon, suggesting that $\beta$-hydrogen activation process occurs competitively with the transammination reaction.

• Proceedings of the Korean Institute of Electrical and Electronic Material Engineers Conference
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• 2008.06a
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• pp.239-240
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• 2008

As semiconductor devices are scaled down for better performance and more functionality, the Cu-based interconnects suffer from the increase of the resistivity of the Cu wires. The resistivity increase, which is attributed to the electron scattering from grain boundaries and interfaces, needs to be addressed in order to further scale down semiconductor devices [1]. The increase in the resistivity of the interconnect can be alleviated by increasing the grain size of electroplating (EP)-Cu or by modifying the Cu surface [1]. Another possible solution is to maximize the portion of the EP-Cu volume in the vias or damascene structures with the conformal diffusion barrier and seed layer by optimizing their deposition processes during Cu interconnect fabrication, which are currently ionized physical vapor deposition (IPVD)-based Ta/TaN bilayer and IPVD-Cu, respectively. The use of in-situ etching, during IPVD of the barrier or the seed layer, has been effective in enlarging the trench volume where the Cu is filled, resulting in improved reliability and performance of the Cu-based interconnect. However, the application of IPVD technology is expected to be limited eventually because of poor sidewall step coverage and the narrow top part of the damascene structures. Recently, Ru has been suggested as a diffusion barrier that is compatible with the direct plating of Cu [2-3]. A single-layer diffusion barrier for the direct plating of Cu is desirable to optimize the resistance of the Cu interconnects because it eliminates the Cu-seed layer. However, previous studies have shown that the Ru by itself is not a suitable diffusion barrier for Cu metallization [4-6]. Thus, the diffusion barrier performance of the Ru film should be improved in order for it to be successfully incorporated as a seed layer/barrier layer for the direct plating of Cu. The improvement of its barrier performance, by modifying the Ru microstructure from columnar to amorphous (by incorporating the N into Ru during PVD), has been previously reported [7]. Another approach for improving the barrier performance of the Ru film is to use Ru as a just seed layer and combine it with superior materials to function as a diffusion barrier against the Cu. A RulTaN bilayer prepared by PVD has recently been suggested as a seed layer/diffusion barrier for Cu. This bilayer was stable between the Cu and Si after annealing at $700^{\circ}C$ for I min [8]. Although these reports dealt with the possible applications of Ru for Cu metallization, cases where the Ru film was prepared by atomic layer deposition (ALD) have not been identified. These are important because of ALD's excellent conformality. In this study, a bilayer diffusion barrier of Ru/TaCN prepared by ALD was investigated. As the addition of the third element into the transition metal nitride disrupts the crystal lattice and leads to the formation of a stable ternary amorphous material, as indicated by Nicolet [9], ALD-TaCN is expected to improve the diffusion barrier performance of the ALD-Ru against Cu. Ru was deposited by a sequential supply of bis(ethylcyclopentadienyl)ruthenium [Ru$(EtCp)_2$] and $NH_3$plasma and TaCN by a sequential supply of $(NEt_2)_3Ta=Nbu^t$ (tert-butylimido-trisdiethylamido-tantalum, TBTDET) and $H_2$ plasma. Sheet resistance measurements, X-ray diffractometry (XRD), and Auger electron spectroscopy (AES) analysis showed that the bilayer diffusion barriers of ALD-Ru (12 nm)/ALD-TaCN (2 nm) and ALD-Ru (4nm)/ALD-TaCN (2 nm) prevented the Cu diffusion up to annealing temperatures of 600 and $550^{\circ}C$ for 30 min, respectively. This is found to be due to the excellent diffusion barrier performance of the ALD-TaCN film against the Cu, due to it having an amorphous structure. A 5-nm-thick ALD-TaCN film was even stable up to annealing at $650^{\circ}C$ between Cu and Si. Transmission electron microscopy (TEM) investigation combined with energy dispersive spectroscopy (EDS) analysis revealed that the ALD-Ru/ALD-TaCN diffusion barrier failed by the Cu diffusion through the bilayer into the Si substrate. This is due to the ALD-TaCN interlayer preventing the interfacial reaction between the Ru and Si.

• Korean Journal of Materials Research
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• v.10 no.3
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• pp.199-203
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• 2000

$Ta_2_O5$ and $Sr_0.8Bi_2.4Ta_2O_9$ films were deposited on p-type Si(100) substrates by a rf-magnetron sputtering and the metal organic decomposition (MOD), respectively.The electrical characteristics of the $Pt/SBT/Ta_2O_5/Si$ structure were obtained as the functions of $O_2$ gas flow ratio during the $Ta_2_O5$ sputtering and $Ta_2_O5$ thickness. And to certify the role of $Ta_2_O5$ as a buffer layer, the electrical characteristics of $Pt/SBT/Ta_2O_5/Si$ were compared. $Pt/SBT/Ta_2O_5/Si$ capacitor with 20% $O_2$ gas flow ratio during the $Ta_2_O5$ sputtering did now show typical C-V curve of metal/ferroelectric/insulator/semiconductor (MFIS) structure. The capacitor with 20% $O_2$ gas flow ratio during the $Ta_2_O5$ sputtering had the largest memory window. And the memory window was decreased as the $Ta_2_O5$ gas flow ratio during the $Ta_2_O5$ sputtering was increased to 40%, 60%. In the C-V characteristics of the $Pt/SBT/Ta_2O_5/Si$ capacitors with the different $Ta_2_O5$ thickness, the capacitor with 26nm thickness of $Ta_2_O5$ had the largest memory window. The C-V and leakage current characteristics of the Pt/SBT/Si structure were worse than those of $Pt/SBT/Ta_2O_5/Si$ structure. These results and Auger electron spectroscopy (AES) measurement showed that $Ta_2_O5$ films as a buffer layer tool a role to prevent from the formation of intermediate phase and interdiffusion between SBT and Si.