Ho Chuen, Qiao Rui, Heng Jiunn B, Chatterjee Aveek, Timp Rolf J, Aluru Narayana R, Timp Gregory
Department of Electrical and Computer Engineering, University of Illinois, Urbana, IL 61801, USA.
Proc Natl Acad Sci U S A. 2005 Jul 26;102(30):10445-50. doi: 10.1073/pnas.0500796102. Epub 2005 Jul 14.
We have produced single, synthetic nanometer-diameter pores by using a tightly focused, high-energy electron beam to sputter atoms in 10-nm-thick silicon nitride membranes. Subsequently, we measured the ionic conductance as a function of time, bath concentration, and pore diameter to infer the conductivity and ionic mobility through the pores. The pore conductivity is found to be much larger than the bulk conductivity for dilute bath concentrations, where the Debye length is larger than the pore radius, whereas it is comparable with or less than the bulk for high bath concentrations. We interpret these observations by using multiscale simulations of the ion transport through the pores. Molecular dynamics is used to estimate the ion mobility, and ion transport in the pore is described by the coupled Poisson-Nernst-Planck and the Stokes equations that are solved self-consistently for the ion concentration and velocity and electrical potential. We find that the measurements are consistent with the presence of fixed negative charge in the pore wall and a reduction of the ion mobility because of the fixed charge and the ion proximity to the pore wall.
我们通过使用紧密聚焦的高能电子束溅射10纳米厚的氮化硅膜中的原子,制备出了单个的、合成的纳米直径孔隙。随后,我们测量了离子电导随时间、浴液浓度和孔径的变化,以推断通过孔隙的电导率和离子迁移率。对于稀浴液浓度,德拜长度大于孔隙半径,发现孔隙电导率远大于本体电导率,而对于高浴液浓度,孔隙电导率与本体电导率相当或小于本体电导率。我们通过对离子通过孔隙的传输进行多尺度模拟来解释这些观察结果。分子动力学用于估计离子迁移率,孔隙中的离子传输由耦合的泊松-能斯特-普朗克方程和斯托克斯方程描述,这些方程针对离子浓度、速度和电势进行自洽求解。我们发现测量结果与孔隙壁中存在固定负电荷以及由于固定电荷和离子靠近孔隙壁导致离子迁移率降低相一致。