• 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.

• Journal of the Mineralogical Society of Korea
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• v.16 no.2
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• pp.135-149
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• 2003

Domestic zeolite ores are mostly composed of Ca-type clinoptilolite, accompanying a little amounts of mordenite. However, other types of zeolite ores rich in ferrierite, heulandite, or mordenite are less commonly found. Based on the quantitative XRD analysis, zeolite contents are determined to be nearly 50∼90 wt%. Impurities (mostly ＞ 10 wt%) in the zeolite ores chiefly consist of quartz, feldspar, smectite, and opal-CT. The determined CEC values ($CEC_{AA}$ ) of powdery samples (grain size: < 125 $\mu\textrm{m}$) of zeolite ores by the Ammonium Acetate method are mostly higher than 100 meq/100 g. Some zeolites from the Guryongpo area, corresponding to the clinoptilolite ore, are measured to be dominantly high in CEC values ranging 170∼190 meq/100 g. Cation exchange property of the zeolite ores varies greatly depending on the types or zeolite species present in the ores. Despite of the lower grade in zeolite content, the $CEC_{AA}$ of ferrierite ore is comparatively high. Compared to this, the $CEC_{AA }$ of heulandite ore is very low, though the zeolite ore exhibits the highest grade ranging up to about 90 wt%. In addition, the CEC values calculated theoretically from the framework composition of clinoptilolite-heulandite series are not consistent with those determined by the cation exchage experiment. The measured $CEC_{AA}$ of clinoptilolite ores are generally higher than those of heulandite ores. This may be due to the higher Ca abundance in exchangeable cation composition and the presence of probable stacking faults in heulandite. The variation of $CEC_{CEC}$ is roughly proportional, though not strictly compatible, to the zeolite contents in clinoptilolite ores. It seems to be caused by the fact that the $CEC_{AA}$ of clinoptilolite locally varies depending on crystal-chemical diversity, i. e., the variation in framework composition (Si/Al) and exchangeable cation composition (especially, the contents of Ca and K). In addition, the determined CEC values ($CEC_{MB}$ ) of zeolite ores by the Methylene Blue method are much higher than those calculated from smectite contents. It suggests a probable reaction of Methylene Blue ion ($C_{16}$ $H_{18}$ $N_3$S+) with larger-pore zeolites than clinoptlolite-heulandite series, i.e., ferrierite and mordenite as well as with smectite. This can be supported by the fact that the ferrierite ore accompanying little amount of smectite has the highest value in CE $C_{MB}$ .

• Journal of the Korean Vacuum Society
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• v.18 no.6
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• pp.459-467
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• 2009

$Cd_2GeSe_4$ and $Cd_2GeSe_4:Co^{2+}$ films were prepared on indium-tin-oxide(ITO)-coated glass substrates by using thermal evaporation. The crystallization was achieved by annealing the as-deposited films in flowing nitrogen. X-ray diffraction spectra showed that the $Cd_2GeSe_4$ and the $Cd_2GeSe_4:Co^{2+}$ films were preferentially grown along the (113) orientation. The crystal structure was rhomohedral(hexagonal) with lattice constants of $a=7.405\;{\AA}$ and $c=36.240\;{\AA}$ for $Cd_2GeSe_4$ and $a=7.43\;{\AA}$ and $c=36.81\;{\AA}$ for $Cd_2GeSe_4:Co^{2+}$ films. From the scanning electron microscope images, the $Cd_2GeSe_4$ and $Cd_2GeSe_4:Co^{2+}$ films were plated, and the grain size increased with increasing annealing temperature. The optical energy band gap, measured at room temperature, of the as-deposited $Cd_2GeSe_4$ films was 1.70 eV and increased to about 1.74 eV and of the as-deposited $Cd_2GeSe_4:Co^{2+}$ films was 1.79 eV and decreased to about 1.74 eV upon annealing in flowing nitrogen at temperatures from $200^{\circ}C$ to $500^{\circ}C$. The dynamical behavior of the charge carriers in the $Cd_2GeSe_4$ and $Cd_2GeSe_4:Co^{2+}$ films were investigated by using the photoinduced discharge characteristics technique.