Search

Crystallization is at the heart of many industrial processes in pharmaceuticals, dyes and pigments, microelectronics, and emerging wearable sensors. This paper reviews nucleation and early-stage crystal growth activated by an electrical pulse at microelectrodes and nanoelectrodes. We review thermodynamic and kinetic theories of electrochemistry developed around microelectrodes. We describe various methods to make microelectrodes and nanoelectrodes. Fundamental understanding is still needed for predicting and controlling nucleation and early-stage crystal growth. Using nanoelectrodes, nucleation and growth kinetics can be studied on one nucleation site at a time. In contrast, on macroelectrodes, nanoparticles are nucleated at random sites and at different times. This gives rise to overlapping growth zones resulting in inhomogeneous particle deposition and growth. The random size and density distributions prevent electrodeposition from being widely adopted as a manufacturing tool for making nanodevices. We describe advances in electrodeposition of metal nanoparticles and organic charge-transfer complexes on micro/nanoelectrodes. We anticipate increased interests in applying electrochemistry for making nanodevices particularly nanosensors and nanosensor arrays. These electrochemically fabricated nanosensor arrays will in turn fulfill the promise of nanoelectrodes as the most advanced analytical tools for medical diagnostics, environmental monitoring, and renewable energy.

Major barriers for commercializing nanowire sensors are complicated synthesis technique and lack of scalable device assembly methods. Charge transfer salts (CTS), like tetrathiafulvalene bromide (TTFBr), have been well known for unique electric and chemical property. This talk will bring a controlled one-step deposition method to fabricate CTS nanowire sensors. By applying certain potentials to designed substrates, TTFBr nanowires can be directly deposited onto the electrodes. Varying deposition conditions and design of substrates are able to control the geometry, density and composition of TTFBr nanowires. TTFBr nanowire sensor shows high sensitivity, selectivity, and fast response towards ammonia gas. The detection limit is less than 1ppm and the response time, at room temperature, is less than 1 minute. Other CTS, like Cu- tetracyanoquinodimethane, can also be fabricated into nanowire sensor using the same method. This research shows a promising scalable fabrication method for various nanowire sensors and is being commercialized.

This talk will focus on substrate-mediated nucleation and crystal growth of organic charge-transfer salt crystals and its application towards scalable manufacturing of nanowire sensors. Nanowires are widely recognized as the next generation building block for ultrasensitive and ultrafast chemical detection. Despite the research progress very few nanowire sensors have reached the market due to their manufacturing complexity. We are exploring a simple, low-cost electrocrystallization method to deposit nanowires from a solution droplet at room temperature directly on electronic substrates. We observed a phenomenon of 1-D crystal growth on nucleation seeds of small sizes. While the 1-D nanostructures resemble those produced by vapor-liquid-solid (VLS) or solution-liquid-solid (SLS) methods, their growth mechanisms are completely different. In our case, the small nanoparticle seed size (or radius of curvature) is responsible for the small size and 1-D growth of the organic crystals. We now apply the seed-mediated mechanism for the electrocrystallization of charge-transfer salt nanowires as small as 7 nm in diameter. The organic-based charge-transfer salt crystals are an underutilized class of sensor materials compared to carbon nanotubes (CNTs), conducting polymers, and metal oxides. We are also prototyping a gas sensor for ammonia detection by nanowire electrocrystallization on electrode patterns. Our approach significantly deviates from the current competing technologies, which involve complex, multistep fabrication and surface modification procedures. We have made nanowire sensors using different charge-transfer materials including tetrathiafulvalene charge-transfer salts and tetracyanoplatinate salts. We improve control of the nanowire deposition by applied potential, reactant concentration, and surface pattern. These nanowire materials show partial selectivity towards ammonia, ethanol, and other volatile organic compounds. We show further improvement in selectivity by the construction of a sensor array and machine learning to extra sensor data from the impedance spectra of more than one type of sensors.