催化反应对低磨料浓度化学机械平坦化的影响

通过低磨料浓度下催化反应对铜膜抛光速率的影响,证实了纳米SiO2胶体作为催化反应物可以极大地提高铜膜表面的化学反应速率。通过浸泡在不同磨料浓度抛光液中的铜电极表面腐蚀电位和腐蚀电流数值,进一步证实了催化反应能够加速凹处钝化膜的生成,并确定了在静态腐蚀条件下催化反应速率转换临界点所对应的纳米SiO2溶胶浓度为0.1vol%和1vol%。根据催化反应对铜晶圆各平坦化参数的影响,确定了低磨料CMP的最佳纳米SiO2溶胶浓度为0.3vol%,此时铜晶圆的抛光速率、台阶消除量、平坦化效率、碟形坑高度和腐蚀坑高度分别为535nm/min、299nm、56%、103nm和19nm。     

多层铜布线CMP后表面残留CuO颗粒的去除研究

This article introduces the removal technology of CuO particles on the post CMP wafer surface of multi-layered copper. According to the Cu film corrosion curve with different concentrations of HEO2 and the effect curve of time on the growth rate of CuO film, CuO film with the thickness of 220 nm grown on Cu a surface was successfully prepared without the interference of CuC12.2H20. Using the static corrosion experiment the type of chelating agent （FA/O II type chelating agent） and the concentration range （10-100 ppm） for CuO removal was determined, and the Cu removal rate was close to zero. The effect of surfactant on the cleaning solution properties was studied, and results indicated that the surfactant has the effect of reducing the surface tension and viscosity of the cleaning solution, and making the cleaning agent more stable. The influence of different concentrations of FA/O I type surfactant and the mixing of FA/O II type chelating agent and FA/O I type surfactant on the CuO removal effect and the film surface state was analyzed. The experimental results indicated that when the concentration of FA/O I type surfactant was 50 ppm, CuO particles were quickly removed, and the surface state was obviously improved. The best removal effect of CuO on the copper wiring film surface was achieved with the cleaning agent ratio of FA/O II type chelating agent 75 ppm and FA/O I type surfactant 50 ppm. Finally, the organic residue on the copper pattern film after cleaning with that cleaning agent was detected, and the results showed that the cleaning used agent did not generate organic residues on the film surface, and effectively removes the organic residue on the water.     

Electrochemical investigation of copper chemical mechanical planarization in alkaline slurry without an inhibitor

This work investigates the static corrosion and removal rates of copper as functions of H202 and FA/OIIconcentration, and uses DC electrochemical measurements such as open circuit potential （OCP）, Tafel ana- lysis, as well as cyclic voltammetry （CV） to study HaOa and FA/OIIdependent surface reactions of Cu coupon electrode in alkaline slurry without an inhibitor. An atomic force microscopy （AFM） technique is also used to measure the surface roughness and surface morphology of copper in static corrosion and polishing conditions. It is shown that 0.5 vol.% H202 should be the primary choice to achieve high material removal rate. The electro- chemical results reveal that the addition of FA/O II can dissolve partial oxide film to accelerate the electrochemical anodic reactions and make the oxide layer porous, so that the structurally weak oxide film can be easily removed by mechanical abrasion. The variation of surface roughness and morphology of copper under static conditions is consistent with and provides further support for the reaction mechanisms proposed in the context of DC electro- chemical measurements. In addition, in the presence of H202, 3 vol.% FA/O II may be significantly effective from a surface roughness perspective to obtain a relatively flat copper surface in chemical mechanical planarization （CMP） process.     

基于SiO2溶胶的稳定性的Cu/SiO2催化体系在化学机械抛光中的应用研究

There is a lot ofhydroxyl on the surface ofnano SiO2 sol used as an abrasive in the chemical mechanical planarization （CMP） process, and the chemical reaction activity of the hydroxyl is very strong due to the nano effect. In addition to providing a mechanical polishing effect, SiO2 sol is also directly involved in the chemical reaction. The stability of SiO2 sol was characterized through particle size distribution, zeta potential, viscosity, surface charge and other parameters in order to ensure that the chemical reaction rate in the CMP process, and the surface state of the copper film after CMP was not affected by the SiO2 sol. Polarization curves and corrosion potential of different concentrations of SiO2 sol showed that trace SiO2 sol can effectively weaken the passivation film thickness. In other words, SiO2 sol accelerated the decomposition rate of passive film. It was confirmed that the SiO2 sol as reactant had been involved in the CMP process of copper film as reactant by the effect of trace SiO2 sol on the removal rate of copper film in the CMP process under different conditions. In the CMP process, a small amount of SiO2 sol can drastically alter the chemical reaction rate of the copper film, therefore, the possibility that Cu/SiO2 as a catalytic system catalytically accelerated the chemical reaction in the CMP process was proposed. According to the van＇t Hoff isotherm formula and the characteristics of a catalyst which only changes the chemical reaction rate without changing the total reaction standard Gibbs free energy, factors affecting the Cu/SiO2 catalytic reaction were derived from the decomposition rate of Cu （OH）2 and the pH value of the system, and then it was concluded that the CuSiO3 as intermediates of Cu/SiO2 catalytic reaction accelerated the chemical reaction rate in the CMP process. It was confirmed that the Cu/SiO2 catalytic system generated the intermediate of the catalytic reaction （CuSiO3） in the CMP process through the removal rate of copper film, infrared spectrum and AFM diagrams in different pH conditions. FinalLy it is concluded that the SiO2 sol used in the experiment possesses stable performance; in the CMP process it is directly involved in the chemical reaction by creating the intermediate of the catalytic reaction （CuSiO3） whose yield is proportional to the pH value, which accelerates the removal of copper film.