AbstractManufacturing custom three-dimensional (3D) carbon functional materials is of utmost importance for applications ranging from electronics and energy devices to medicine, and beyond. In lieu of viable eco-friendly synthesis pathways, conventional methods of carbon growth involve energy-intensive processes with inherent limitations of substrate compatibility. The yearning to produce complex structures, with ultra-high aspect ratios, further impedes the quest for eco-friendly and scalable paths toward 3D carbon-based materials patterning. Here, we demonstrate a facile process for carbon 3D printing at room temperature, using low-power visible light and a metal-free catalyst. Within seconds to minutes, this one-step photocatalytic growth yields rod-shaped microstructures with aspect ratios up to ~500 and diameters below 10 μm. The approach enables the rapid patterning of centimeter-size arrays of rods with tunable height and pitch, and of custom complex 3D structures. The patterned structures exhibit appealing luminescence properties and ohmic behavior, with great potential for optoelectronics and sensing applications, including those interfacing with biological systems.

Defect engineering in two-dimensional materials expands the realm of their applications in catalysis, nanoelectronics, sensing, and beyond. As limited tools are available to explore nanoscale functional properties in non-vacuum environments, theoretical modeling provides some invaluable insight into the effect of local deformations to deepen the understanding of experimental signals acquired by nanoscale chemical imaging. We demonstrate the controlled creation of nanoscale strained defects in hexagonal boron nitride (h-BN) using atomic force microscopy and infrared (IR) light under an inert environment. Nanoscale IR spectroscopy reveals the broadening of the in-plane phonon (E1u) mode of h-BN during defect formation while density functional theory-based calculations and molecular dynamics provide quantification of the tensile and compressive strain in the deformation.

A multicrystalline silicon solar cell was analyzed using Raman microspectroscopy. We measured the prominent Raman modes of silicon, nanocrystalline silicon and silver oxide in various regions of the solar cell to generate insights into the process and material quality of the finished device. First, by comparing the distribution of the transverse optical (TO) phonon peak position and full-width-at-half-maximum (FWHM) of the solar cell with a single crystal silicon wafer, the quality of the multicrystalline silicon surface was ascertained. Second, a similar analysis of the remnant saw marks on the device surface showed a discernably higher and wider distribution of TO phonon peak position and FWHM compared to a multicrystalline silicon surface. This indicated the presence of residual compressive stresses in the saw mark region. Third, by observing the silver fingers and bus bars, a residual silver oxide layer was identified, up to 25 μm away from the line edges. This was attributed to the screen printing of the silver paste and the subsequent firing process. Finally, Raman mapping on an embedded inclusion showed the presence of nanocrystalline silicon phase. The multicrystalline silicon region surrounding the inclusion was under tensile stress. A nondestructive, confocal Raman analysis of the inclusion provided a 3-D visualization of the defect, both inside and above the surface of the multicrystalline silicon wafer.

Tailoring two-dimensional (2D) materials functionalities is closely intertwined with defect engineering. Conventional methods do not offer the necessary control to locally introduce and study defects in 2D materials, especially in non-vacuum environments. Here, an infrared pulsed laser focused under the metallic tip of an atomic force microscope cantilever is used to create nanoscale defects in hexagonal boron nitride (h-BN) and to subsequently investigate the induced lattice distortions by means of nanoscale infrared (nano-IR) spectroscopy. The effects of incoming light power, exposure time, and environmental conditions on the defected regions are considered. Nano-IR spectra complement the morphology maps by revealing changes in lattice vibrations that distinguish the defects formed under various environments. This work introduces versatile experimental avenues to trigger and probe local reactions that functionalize 2D materials through defect creation with a higher level of precision for applications in sensing, catalysis, optoelectronics, quantum computing, and beyond.

Scanning tunneling microscopy and spectroscopy (STM/STS) are used to electronically switch atomically-thin memristors, referred to as “atomristors”, based on a graphene/molybdenum disulfide (MoS_2)/Au heterostructure. A gold-assisted exfoliation method was used to produce near-millimeter (mm) scale MoS_2 on Au thin-film substrates, followed by transfer of a separately exfoliated graphene top layer. Our results reveal that it is possible to switch the conductivity of a graphene/MoS_2/Au memristor stack using an STM tip. These results provide a path to further studies of atomically-thin memristors fabricated from heterostructures of two-dimensional materials such as graphene and transition metal dichalcogenides (TMDs).

The use of hexagonal boron nitride (h-BN) as a non-metal heterogeneous catalyst has been a popular subject in research since the discovery of its catalytic properties in 2016. Previous work found that an activation step was necessary for producing an effective catalyst. Density functional theory (DFT) calculations indicate defect sites, such as nitrogen (VN) and boron (VB) vacancies, bind favourably to olefins, hydrogen, and oxygen. In particular, the visible fluorescence intensity of processed h-BN increased with the length of exposure to air. The fluorescence behaviour of dh-BN powders when exposed to air after exposure to species such as argon, propene, and carbon dioxide is presented. Density of state calculations for molecular and atomic oxygen bound to VN and VB show that this increase in fluorescence may be due to atomic oxygen binding to VN. The fluorescence emission behaviour observed in dh-BN powders and its relationship to DOS of oxygen species bound to catalytically active defect sites provides a better understanding of potential deactivation modes for catalysts based on dh-BN.