Ink-Lithography for Property Engineering and Patterning of Nanocrystal Thin Films.

Next-generation devices and systems require the development and integration of advanced materials, the realization of which inevitably requires two separate processes: property engineering and patterning. Here, we report a one-step, ink-lithography technique to pattern and engineer the properties of thin films of colloidal nanocrystals that exploits their chemically addressable surface. Colloidal nanocrystals are deposited by solution-based methods to form thin films and a local chemical treatment is applied using an ink-printing technique to simultaneously modify (i) the chemical nature of the nanocrystal surface to allow thin-film patterning and (ii) the physical electronic, optical, thermal, and mechanical properties of the nanocrystal thin films. The ink-lithography technique is applied to the library of colloidal nanocrystals to engineer thin films of metals, semiconductors, and insulators on both rigid and flexible substrates and demonstrate their application in high-resolution image replications, anticounterfeit devices, multicolor filters, thin-film transistors and circuits, photoconductors, and wearable multisensors.

Designing Surface Chemistry of Silver Nanocrystals for Radio Frequency Circuit Applications.

We introduce solution-based, room temperature- and atmospheric pressure-processed silver nanocrystal (Ag NC)-based electrical circuits and interconnects for radio frequency (RF)/microwave frequency applications. We chemically designed the surface and interface states of Ag NC thin films to achieve high stability, dc and ac conductivity, and minimized RF loss through stepwise ligand exchange, shell coating, and surface cleaning. The chemical and structural properties of the circuits and interconnects affect the high-frequency electrical performance of Ag NC thin films, as confirmed by high-frequency electromagnetic field simulations. An all solution-based process is developed to build coplanar structures, in which Ag NC thin films are positioned at both sides of the substrates. In addition, we fabricated flexible transmission lines and broadband electrical circuits for resistors, interdigitated capacitors, spiral and omega-shaped inductors, and patch antennas with maximum inductance and capacitance values of 3 nH and 2.5 pF at frequencies up to 20 GHz. We believe that our approach will lead to a cost-effective realization of RF circuits and devices in which sensing and wireless communication capabilities are combined for internet-of-things applications.

Chemically Engineered Au-Ag Plasmonic Nanostructures to Realize Large Area and Flexible Metamaterials.

We developed a simple and systematic method to fabricate optically tunable and thermally and chemically stable Au-Ag nanocrystal-based plasmonic metamaterials. An Ag nanocrystal-based metamaterial with desirable optical properties was fabricated via nanoimprinting and ligand-exchange process. Its optical properties were controlled by selectively substituting Ag atoms with Au atoms through a spontaneous galvanic replacement reaction. The developed Au-Ag-based metamaterials provide excellent tunable plasmonic properties required for various applications in the visible and near-infrared regions by controlling the Au-Ag composition according to the conditions of the galvanic displacement. Furthermore, their thermal and chemical stabilities significantly improved because of the protective Au thin layer on the surface. Using this developed process, chemically and thermally stable and flexible plasmonic metamaterials were successfully fabricated on a flexible polyester terephthalate substrate.

Transition States of Nanocrystal Thin Films during Ligand-Exchange Processes for Potential Applications in Wearable Sensors.

Ligand exchange is an advanced technique for tuning the various properties of nanocrystal (NC) thin films, widely used in the NC thin-film device applications. Understanding how the NC thin films transform into functional thin-film devices upon ligand exchange is essential. Here, we investigated the process of structural transformation and accompanying property changes in the NC thin films, by monitoring the various characteristics of silver (Ag) NC thin films at each stage of the ligand-exchange process. A transition state was identified in which the ligands are partially exchanged, where the NC thin films showed unexpected electromechanical features with high gauge factors up to 300. A model system was established to explain the origin of the high gauge factors, supported by the observation of spontaneously formed nanocracks and metal-insulator transition from the structural analysis and charge transport study, respectively. Taking advantages of the unique electromechanical properties of the NC thin films, we fabricated flexible strain gauge sensor devices with high sensitivity, reliability, and stability. We introduce a one-step fabrication process, namely, "the time- and spatial-selective ligand-exchange process", for the design of low-cost and high-performance wearable sensors that effectively detect human motion, such as finger or neck muscle movement. This study provides a fundamental understanding of the ligand-exchange process in NCs, as well as an insight into the functionalities of the NC thin films for technological applications.

Chemically Designed Metallic/Insulating Hybrid Nanostructures with Silver Nanocrystals for Highly Sensitive Wearable Pressure Sensors.

With the increase in interest in wearable tactile pressure sensors for e-skin, researches to make nanostructures to achieve high sensitivity have been actively conducted. However, limitations such as complex fabrication processes using expensive equipment still exist. Herein, simple lithography-free techniques to develop pyramid-like metal/insulator hybrid nanostructures utilizing nanocrystals (NCs) are demonstrated. Ligand-exchanged and unexchanged silver NC thin films are used as metallic and insulating components, respectively. The interfaces of each NC layer are chemically engineered to create discontinuous insulating layers, i.e., spacers for improved sensitivity, and eventually to realize fully solution-processed pressure sensors. Device performance analysis with structural, chemical, and electronic characterization and conductive atomic force microscopy study reveals that hybrid nanostructure based pressure sensor shows an enhanced sensitivity of higher than 500 kPa-1, reliability, and low power consumption with a wide range of pressure sensing. Nano-/micro-hierarchical structures are also designed by combining hybrid nanostructures with conventional microstructures, exhibiting further enhanced sensing range and achieving a record sensitivity of 2.72 × 104 kPa-1. Finally, all-solution-processed pressure sensor arrays with high pixel density, capable of detecting delicate signals with high spatial selectivity much better than the human tactile threshold, are introduced.

Designing Metallic and Insulating Nanocrystal Heterostructures to Fabricate Highly Sensitive and Solution Processed Strain Gauges for Wearable Sensors.

All-solution processed, high-performance wearable strain sensors are demonstrated using heterostructure nanocrystal (NC) solids. By incorporating insulating artificial atoms of CdSe quantum dot NCs into metallic artificial atoms of Au NC thin film matrix, metal-insulator heterostructures are designed. This hybrid structure results in a shift close to the percolation threshold, modifying the charge transport mechanism and enhancing sensitivity in accordance with the site percolation theory. The number of electrical pathways is also manipulated by creating nanocracks to further increase its sensitivity, inspired from the bond percolation theory. The combination of the two strategies achieves gauge factor up to 5045, the highest sensitivity recorded among NC-based strain gauges. These strain sensors show high reliability, durability, frequency stability, and negligible hysteresis. The fundamental charge transport behavior of these NC solids is investigated and the combined site and bond percolation theory is developed to illuminate the origin of their enhanced sensitivity. Finally, all NC-based and solution-processed strain gauge sensor arrays are fabricated, which effectively measure the motion of each finger joint, the pulse of heart rate, and the movement of vocal cords of human. This work provides a pathway for designing low-cost and high-performance electronic skin or wearable devices.

Engineering the Charge Transport of Ag Nanocrystals for Highly Accurate, Wearable Temperature Sensors through All-Solution Processes.

All-nanocrystal (NC)-based and all-solution-processed wearable resistance temperature detectors (RTDs) are introduced. The charge transport mechanisms of Ag NC thin films are engineered through various ligand treatments to design high performance RTDs. Highly conductive Ag NC thin films exhibiting metallic transport behavior with high positive temperature coefficients of resistance (TCRs) are achieved through tetrabutylammonium bromide treatment. Ag NC thin films showing hopping transport with high negative TCRs are created through organic ligand treatment. All-solution-based, one-step photolithography techniques that integrate two distinct opposite-sign TCR Ag NC thin films into an ultrathin single device are developed to decouple the mechanical effects such as human motion. The unconventional materials design and strategy enables highly accurate, sensitive, wearable and motion-free RTDs, demonstrated by experiments on moving or curved objects such as human skin, and simulation results based on charge transport analysis. This strategy provides a low cost and simple method to design wearable multifunctional sensors with high sensitivity which could be utilized in various fields such as biointegrated sensors or electronic skin.