Nanoporous-Gold-Based Electrode Morphology Libraries for Investigating Structure-Property Relationships in Nucleic Acid Based Electrochemical Biosensors.

Nanoporous gold (np-Au) electrode coatings significantly enhance the performance of electrochemical nucleic acid biosensors because of their three-dimensional nanoscale network, high electrical conductivity, facile surface functionalization, and biocompatibility. Contrary to planar electrodes, the np-Au electrodes also exhibit sensitive detection in the presence of common biofouling media due to their porous structure. However, the pore size of the nanomatrix plays a critical role in dictating the extent of biomolecular capture and transport. Small pores perform better in the case of target detection in complex samples by filtering out the large nonspecific proteins. On the other hand, larger pores increase the accessibility of target nucleic acids in the nanoporous structure, enhancing the detection limits of the sensor at the expense of more interference from biofouling molecules. Here, we report a microfabricated np-Au multiple electrode array that displays a range of electrode morphologies on the same chip for identifying feature sizes that reduce the nonspecific adsorption of proteins but facilitate the permeation of target DNA molecules into the pores. We demonstrate the utility of the electrode morphology library in studying DNA functionalization and target detection in complex biological media with a special emphasis on revealing ranges of electrode morphologies that mutually enhance the limit of detection and biofouling resilience. We expect this technique to assist in the development of high-performance biosensors for point-of-care diagnostics and facilitate studies on the electrode structure-property relationships in potential applications ranging from neural electrodes to catalysts.

In situ electrical modulation and monitoring of nanoporous gold morphology.

The ability to fine-tune feature size in nanostructured thin films is critical, as many desirable properties of these materials are dictated by their nanostructure. Accordingly, there is a need for techniques that allow for modifying nanostructure while monitoring the morphological changes in situ. Here, we demonstrate a closed-loop electro-annealing system which enables in situ monitoring of morphology evolution in sub-micron nanoporous gold (np-Au) thin films. Np-Au is produced by a microfabrication-compatible self-assembly process that produces a network of interconnected ligaments with tunable diameter (10 s to 100 s of nanometers), making it a desirable material for numerous applications and fundamental studies alike. We specifically investigate the relationship between np-Au morphology (i.e., ligament diameter) and electrical resistance of the thin film. A strong correlation emerges between ligament size and electrical resistance, which puts forward resistance as an effective parameter for monitoring morphology evolution. Surprisingly, np-Au films with thicker ligaments lead to an increase in electrical resistance, which is unexpected since the extent of charge carrier scattering at the ligament surface should decrease with increasing ligament size. Further examination of np-Au morphology with high-resolution electron microscopy revealed grain growth on the ligaments in highly-annealed np-Au thin films. This suggests that grains act as scattering centers for charge carriers and this becomes the dominant mechanism in dictating electrical resistance in a percolated network of thin conductive ligaments.

Nanoscale Probing of Local Electrical Characteristics on MBE-Grown Bi2Te3 Surfaces under Ambient Conditions.

The local electrical characteristics on the surface of MBE-grown Bi2Te3 are probed under ambient conditions by conductive atomic force microscopy. Nanoscale mapping reveals a 10-100× enhancement in current at step-edges compared to that on terraces. Analysis of the local current-voltage characteristics indicates that the transport mechanism is similar for step-edges and terraces. Comparison of the results with those for control samples shows that the current enhancement is not a measurement artifact but instead is due to local differences in electronic properties. The likelihood of various possible mechanisms is discussed. The absence of enhancement at the step-edges for graphite terraces is consistent with the intriguing possibility that spin-orbit coupling and topological effects play a significant role in the step-edge current enhancement in Bi2Te3.