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Pulsed metalorganic chemical vapor deposition (MOCVD) of conformal copper
seed layers, for the electrodeposition Cu films, has been achieved by an
alternating supply of a Cu(I) source and H2 reactant at the
deposition temperatures of 50 - 100°C. The Cu thickness increased
proportionally to the number of cycle, and the growth rate was in the range
of 3.5 to 8.2 A /cycle, showing the ability to control the nano-scale
thickness. As-deposited films show highly smooth surfaces even for more than
100nm. In addition, about a 90% step coverage was obtained inside trenches,
with an aspect ratio greater than 30:1. H2, introduced as a
reactant gas, can play an active role in achieving highly conformal
coatings, with increased grain sizes.
The effect of Mg in Ag(Mg)/SiO2/Si multilayers on the adhesion, passivation, and resistivity following vacuum annealing at 200–500 °C has been investigated. The annealing of Ag(Mg)/SiO2/Si multilayers produced surface and interfacial MgO layers, resulting in a MgO/Ag/MgO/SiO2/Si structure. The formation of a surface MgO/Ag bilayer structure provided excellent passivation against air and CF4 plasma chemistry. In addition, the adhesion of Ag to SiO2 was improved due to the formation of an interfacial MgO layer resulting from the reaction of segregated Mg with SiO2. However, the negligible solubility of Si in Ag prevented the dissolution of free silicon into the Ag(Mg) film produced from the reaction Mg + SiO2 = MgO + free Si, which in turn limited the reaction between Mg and SiO2, which led to a decrease in the adhesion of Ag to SiO2 at the higher temperature. The use of an O2 plasma prior to Ag(Mg) alloy deposition on SiO2 produced an oxygen-rich surface on the SiO2, which allowed for the enhanced reaction of the segregated Mg and SiO2 at the surface, thus resulting in markedly increased adhesion properties.
A self-aligned surface MgO layer was used as a mask for dry etching the Cu(Mg) alloy films using an O2 plasma and H(hfac) chemistry. The surface MgO layer was formed by diffusion of Mg from Cu film to the free surface. Cu(4.5at%Mg) film having thickness of 300nm was annealed in O2 ambient at 10 mTorr, 500°C for 30min, followed by the patterning of the MgO layer using photolithography and HF wet etch process. The patterned MgO layer successfully served as a hard mask for dry etching the Cu(Mg) alloy films with a taper slope. In addition, the high quality self-aligned MgO layer was formed upon annealing the Cu(4.5 at.% Mg) alloy films at the low temperature of 300°C. Furthermore, the surface MgO layer grown on Cu(2.3at.% Mg) alloy films at 500°C withstood as a hard mask for dry etching, and thus achieving the patterned copper alloy lines with the low resistivity of 2.2 μΩ-cm. Consequently, this novel etch process using a self-aligned MgO mask can be used for patterning the low resistivity copper alloy lines with a low thermal budget, which is suitable for large-size TFT-LCDs.
The effect of Mg in Ag(Mg)/SiO2/Si multilayers on adhesion, agglomeration, and resistivity after annealing in vacuum at 200 to 500 have been investigated. The annealing of Ag(Mg)/SiO2/Si multilayers produced surface and interfacial MgO layers, resulting in MgO/Ag(Mg)/MgO/SiO2/Si structure. The presence of surface MgO provided the passivation against air, thus leading to the significantly enhanced resistance to agglomeration. In addition, the resistivity of Ag(Mg) film decreased by lowering Mg content and increasing the annealing temperature as well. Furthermore, Ag adhesion to SiO2 was improved due to the formation of the interfacial MgO layer resulting from the reaction of segregated Mg with SiO2. Also, the negligible solubility of Si in Ag prevented the dissolution of free silicon produced from the reaction, Mg + SiO2 = MgO + Si, which was in contrast with the dissolution of a significant amount of silicon released from the SiO2 substrate in Cu(Mg)/SiO2/Si multilayers after annealing at high temperature, e.g., 400. The dissolved Si in Cu caused the rapid increase in resistivity in Cu(Mg)/SiO2/Si.
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