Solutions Are the Problem: Ordered Two-Dimensional Covalent Organic Framework Films by Chemical Vapor Deposition.

Covalent organic frameworks (COFs) are a promising class of crystalline polymer networks that are useful due to their high porosity, versatile functionality, and tunable architecture. Conventional solution-based methods of producing COFs are marred by slow reactions that produce powders that are difficult to process into adaptable form factors for functional applications, and there is a need for facile and fast synthesis techniques for making crystalline and ordered covalent organic framework (COF) thin films. In this work, we report a chemical vapor deposition (CVD) approach utilizing co-evaporation of two monomers onto a heated substrate to produce highly crystalline, defect-free COF films and coatings with hydrazone, imine, and ketoenamine COF linkages. This all-in-one synthesis technique produces highly crystalline, 40 nm-1 µm-thick COF films on Si/SiO2 substrates in less than 30 min. Crystallinity and alignment were proven by using a combination of grazing-incidence wide-angle X-ray scattering (GIWAXS) and transmission electron microscopy (TEM), and successful conversion of the monomers to produce the target COF was supported by Raman spectroscopy, X-ray photoelectron spectroscopy (XPS), and UV-vis measurements. Additionally, we used atomic force microscopy (AFM) to investigate the growth mechanisms of these films, showing the coalescence of triangular crystallites into a smooth film. To show the wide applicability and scope of the CVD process, we also prepared crystalline ordered COF films with imine and ketoenamine linkages. These films show potential as high-quality size exclusion membranes, catalytic platforms, and organic transistors.

Non-Linear Optics at Twist Interfaces in h-BN/SiC Heterostructures.

Understanding the emergent electronic structure in twisted atomically thin layers has led to the exciting field of twistronics. However, practical applications of such systems are challenging since the specific angular correlations between the layers must be precisely controlled and the layers have to be single crystalline with uniform atomic ordering. Here, an alternative, simple, and scalable approach is suggested, where nanocrystallinetwo-dimensional (2D) film on 3D substrates yields twisted-interface-dependent properties. Ultrawide-bandgap hexagonal boron nitride (h-BN) thin films are directly grown on high in-plane lattice mismatched wide-bandgap silicon carbide (4H-SiC) substrates to explore the twist-dependent structure-property correlations. Concurrently, nanocrystalline h-BN thin film shows strong non-linear second-harmonic generation and ultra-low cross-plane thermal conductivity at room temperature, which are attributed to the twisted domain edges between van der Waals stacked nanocrystals with random in-plane orientations. First-principles calculations based on time-dependent density functional theory manifest strong even-order optical nonlinearity in twisted h-BN layers. This work unveils that directly deposited 2D nanocrystalline thin film on 3D substrates could provide easily accessible twist-interfaces, therefore enabling a simple and scalable approach to utilize the 2D-twistronics integrated in 3D material devices for next-generation nanotechnology.

A Researcher's Perspective on Unconventional Lab-to-Fab for 2D Semiconductor Devices.

Current silicon technology is on the verge of reaching its performance limits. This aspect, coupled with the global chip shortage, makes a solid case for steering our attention toward the accelerated commercialization of other electronic materials. Among the available suite of emerging electronic materials, two-dimensional materials, including transition metal dichalcogenides (TMDs), exhibit improved short-channel effects, high electron mobility, and integration into CMOS-compatible processing. While these materials may not be able to replace silicon at the current stages of development, they can supplement Si in the form of Si-compatible CMOS processing and be manufactured for tailored applications. However, the major hurdle in the path of commercialization of such materials is the difficulty in producing their wafer-scale forms, which are not necessarily single crystalline but on a large scale. Recent but exploratory interest in 2D materials from industries, such as TSMC, necessitates an in-depth analysis of their commercialization potential based on trends and progress in entrenched electronic materials (Si) and ones with a short-term commercialization potential (GaN, GaAs). We also explore the possibility of unconventional fabrication techniques, such as printing, for 2D materials becoming more mainstream and being adopted by industries in the future. In this Perspective, we discuss aspects to optimize cost, time, thermal budget, and a general pathway for 2D materials to achieve similar milestones, with an emphasis on TMDs. Beyond synthesis, we propose a lab-to-fab workflow based on recent advances that can operate on a low budget with a mainstream full-scale Si fabrication unit.

Unravelling the room temperature growth of two-dimensional h-BN nanosheets for multifunctional applications.

The room temperature growth of two-dimensional van der Waals (2D-vdW) materials is indispensable for state-of-the-art nanotechnology. Low temperature growth supersedes the requirement of elevated growth temperatures accompanied with high thermal budgets. Moreover, for electronic applications, low or room temperature growth reduces the possibility of intrinsic film-substrate interfacial thermal diffusion related deterioration of the functional properties and the consequent deterioration of the device performance. Here, we demonstrated the growth of ultrawide-bandgap boron nitride (BN) at room temperature by using the pulsed laser deposition (PLD) process, which exhibited various functional properties for potential applications. Comprehensive chemical, spectroscopic and microscopic characterizations confirmed the growth of ordered nanosheet-like hexagonal BN (h-BN). Functionally, the nanosheets show hydrophobicity, high lubricity (low coefficient of friction), and a low refractive index within the visible to near-infrared wavelength range, and room temperature single-photon quantum emission. Our work unveils an important step that brings a plethora of potential applications for these room temperature grown h-BN nanosheets as the synthesis can be feasible on any given substrate, thus creating a scenario for "h-BN on demand" under a frugal thermal budget.

Realizing Quantum Technologies in Nanomaterials and Nanoscience.

A brief overview of quantum materials and their prospects for applications, in the near, mid, and far-term in the areas of quantum information science, spintronics, valleytronics, and twistronics and those involving topology are covered in this perspective. The material and processing challenges that will modulate the realism of the applications will be discussed as well.

Structure, Properties and Applications of Two-Dimensional Hexagonal Boron Nitride.

Hexagonal boron nitride (h-BN) has emerged as a strong candidate for two-dimensional (2D) material owing to its exciting optoelectrical properties combined with mechanical robustness, thermal stability, and chemical inertness. Super-thin h-BN layers have gained significant attention from the scientific community for many applications, including nanoelectronics, photonics, biomedical, anti-corrosion, and catalysis, among others. This review provides a systematic elaboration of the structural, electrical, mechanical, optical, and thermal properties of h-BN followed by a comprehensive account of state-of-the-art synthesis strategies for 2D h-BN, including chemical exfoliation, chemical, and physical vapor deposition, and other methods that have been successfully developed in recent years. It further elaborates a wide variety of processing routes developed for doping, substitution, functionalization, and combination with other materials to form heterostructures. Based on the extraordinary properties and thermal-mechanical-chemical stability of 2D h-BN, various potential applications of these structures are described.

Molecular size-dependent subcontinuum solvent permeation and ultrafast nanofiltration across nanoporous graphene membranes.

Selective solvent and solute transport across nanopores is fundamental to membrane separations, yet it remains poorly understood, especially for non-aqueous systems. Here, we design a chemically robust nanoporous graphene membrane and study molecular transport in various organic liquids under subnanometre confinement. We show that the nature of the solvent can modulate solute diffusion across graphene nanopores, and that breakdown of continuum flow occurs when pore size approaches the solvent's smallest molecular cross-section. By holistically engineering membrane support, modelling pore creation and defect management, high rejection and ultrafast organic solvent nanofiltration of dye molecules and separation of hexane isomers are achieved. The membranes exhibit stable fluxes across a range of solvents, consistent with flow across rigid pores whose size is independent of the solvent. These results demonstrate that nanoporous graphene is a rich materials system for controlling subcontinuum flow that could enable new membranes for a range of challenging separation needs.