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Creators/Authors contains: "Unocic, Raymond_R"

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  1. Abstract Controlled fabrication of nanopores in 2D materials offer the means to create robust membranes needed for ion transport and nanofiltration. Techniques for creating nanopores have relied upon either plasma etching or direct irradiation; however, aberration‐corrected scanning transmission electron microscopy (STEM) offers the advantage of combining a sub‐Å sized electron beam for atomic manipulation along with atomic resolution imaging. Here, a method for automated nanopore fabrication is utilized with real‐time atomic visualization to enhance the mechanistic understanding of beam‐induced transformations. Additionally, an electron beam simulation technique, Electron‐Beam Simulator (E‐BeamSim) is developed to observe the atomic movements and interactions resulting from electron beam irradiation. Using the MXene Ti3C2Tx, the influence of temperature on nanopore fabrication is explored by tracking atomic transformations and find that at room temperature the electron beam irradiation induces random displacement and results in titanium pileups at the nanopore edge, which is confirmed by E‐BeamSim. At elevated temperatures, after removal of the surface functional groups and with the increased mobility of atoms results in atomic transformations that lead to the selective removal of atoms layer by layer. This work can lead to the development of defect engineering techniques within functionalized MXene layers and other 2D materials. 
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  2. Abstract The growing demand for flexible and wearable hybrid electronics has triggered the need for advanced manufacturing techniques with versatile printing capabilities. Complex ink formulations, use of surfactants/contaminants, limited source materials, and the need for high‐temperature heat treatments for sintering are major issues facing the current inkjet and aerosol printing methods. Here, the nanomanufacturing of flexible hybrid electronics (FHE) by dry printing silver and indium tin oxide on flexible substrates using a novel laser‐based additive nanomanufacturing process is reported. The electrical resistance of the printed lines is tailored during the print process by tuning the geometry and structure of the printed samples. Different FHE designs are fabricated and tested to check the performance of the devices. Mechanical reliability tests including cycling, bending, and stretching confirm the expected performance of the printed samples under different strain levels. This transformative liquid‐free process allows the on‐demand formation and in situ laser crystallization of nanoparticles for printing pure materials for future flexible and wearable electronics and sensors. 
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  3. Abstract Direct printing of functional materials, structures, and devices on various platforms such as flexible to rigid substrates is of interest for applications ranging from electronics to energy and sensing to biomedical devices. Current additive manufacturing (AM) and printing processes are either limited by the available sources of functional materials or require to be in the form of precisely designed inks. Here, a novel laser‐based additive nanomanufacturing (ANM) system capable of in situ and on‐demand generations of nanoparticles that can serve as nanoscale building blocks for real‐time sintering and dry printing a variety of multifunctional materials and patterns at atmospheric pressure and room temperature is reported. The ability to print different functional materials on various rigid and flexible platforms is shown. This nonequilibrium process involves pulsed laser ablation of targets and in situ formation of pure amorphous nanoparticles’ stream that are guided through a nozzle onto the surface of the substrate, where they are sintered/crystallized in real‐time. Further, the process–structure relationship of the printed materials from nanoscale to microscale is shown. This new ANM concept opens up an opportunity for printing advanced functional materials and devices on rigid and flexible substrates that can be employed both on the earth and in space. 
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  4. Abstract While hexagonal boron nitride (hBN) has been widely used as a buffer or encapsulation layer for emerging electronic devices, interest in utilizing it for large‐area chemical barrier coating has somewhat faded. A chemical vapor deposition process is reported here for the conformal growth of hBN on large surfaces of various alloys and steels, regardless of their complex shapes. In contrast to the previously reported very limited protection by hBN against corrosion and oxidation, protection of steels against 10% HCl and oxidation resistance at 850 °C in air is demonstrated. Furthermore, an order of magnitude reduction in the friction coefficient of the hBN coated steels is shown. The growth mechanism is revealed in experiments on thin metal films, where the tunable growth of single‐crystal hBN with a selected number of layers is demonstrated. The key distinction of the process is the use of N2gas, which gets activated exclusively on the catalyst's surface and eliminates adverse gas‐phase reactions. This rate‐limiting step allowed independent control of activated nitrogen along with boron coming from a solid source (like elemental boron). Using abundant and benign precursors, this approach can be readily adopted for large‐scale hBN synthesis in applications where cost, production volume, and process safety are essential. 
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