Rapid Synthesis of Crystalline COF Films via Cutting-Edge Chemical Vapor Deposition


Two-dimensional covalent organic frameworks (COFs), often abbreviated as 2D COFs, are a class of materials composed of organic building blocks linked together by strong covalent bonds in a two-dimensional plane. 2D COFs are typically made from light elements such as hydrogen, boron, carbon, nitrogen, and oxygen. They are formed by connecting organic molecules through covalent bonds in a repeating, lattice-like pattern. This results in a two-dimensional sheet-like structure. These frameworks are known for their highly ordered and porous structures. The pores in 2D COFs can be precisely designed and controlled, which makes them highly versatile. Due to their porous nature, 2D COFs often have very high surface areas, which is beneficial for various applications like gas storage and separation. The properties of 2D COFs can be finely tuned by changing the organic building blocks and the types of linkages used. This allows for the creation of materials with specific properties suited to particular applications. 2D COFs have potential applications in many fields, including gas storage and separation, catalysis, drug delivery, sensing, and as electrodes in batteries and supercapacitors. Their high surface area and tunable porosity make them particularly useful for applications involving gas absorption and catalytic reactions. The synthesis of 2D COFs typically involves organic synthesis techniques and may include methods like solvothermal reactions, mechanochemical synthesis, or on-surface synthesis. While COFs, in general, are known for their stability, the stability of 2D COFs can vary and is often a key area of research, as it is crucial for their practical application. Due to their ordered structure and the possibility of incorporating various functional groups, 2D COFs can exhibit unique optical and electronic properties, which are being explored for use in electronic devices and photovoltaics. Indeed, 2D covalent organic frameworks represent a fascinating and rapidly developing area of materials science, offering a wide range of potential applications due to their unique structural, chemical, and physical properties.

Traditional methods of synthesizing COFs often result in microcrystalline powders that are insoluble and challenging to process into useful forms. This limitation has hindered the widespread adoption of COFs in practical applications, despite their promising properties. The solution-based methods typically employed are slow and inefficient, leading to a need for alternative approaches that can produce COFs in a more controlled and scalable manner. In a new study published in ACS Nano led by Professor Rafael Verduzco from the Rice University and contributed by Dr. Jeremy Daum, Dr.  Alec Ajnsztajn, Dr.  Sathvik Ajay Iyengar, Dr.  Jacob Lowenstein, Dr.  Soumyabrata Roy, Dr.  Guan-hui Gao, Esther Tsai, and Professor Pulickel Ajayan, the researchers addressed a significant challenge in the synthesis of covalent organic frameworks (COFs), particularly in the form of thin films. Their study, published in ACS Nano Journal in 2023, detailed a novel method for producing COFs using chemical vapor deposition (CVD). Their primary goal was to develop a more efficient and scalable method for synthesizing COF films, which are known for their high porosity, versatile functionality, and tunable architecture. Traditional methods, usually resulting in microcrystalline powders, posed limitations due to their insolubility and difficulty in processing. They utilized a CVD process involving the co-evaporation of two monomers onto a heated substrate. This method contrasts with conventional solution-based approaches, which are slower and less efficient. The CVD technique enabled them to produce highly crystalline, defect-free COF films. These films were created on Si/SiO2 substrates and had thicknesses ranging from 40 nm to 1 μm. Different types of COF linkages, such as hydrazone, imine, and ketoenamine, were synthesized using appropriate monomers.

They employed multiple advanced techniques to characterize the synthesized COF films, ensuring their quality and effectiveness. These included GIWAXS, TEM, Raman spectroscopy, X-ray photoelectron spectroscopy (XPS), and UV-vis measurements. Techniques like AFM were used to investigate the growth mechanisms of these films. The researchers successfully demonstrated the formation of highly ordered, crystalline COF films in a significantly reduced time (less than 30 minutes). They confirmed the crystallinity and alignment of the films using the mentioned characterization techniques. The films showed potential for various applications, including size exclusion membranes, catalytic platforms, and organic transistors.

The new study marked a significant advancement in the field of COF synthesis, offering a faster, more scalable, and environmentally friendly approach compared to existing methods. It opened up new possibilities for the application of COFs in various industrial and technological fields. In essence, the research by Professor Rafael Verduzco and colleagues revolutionized the way COF films are synthesized, addressing a critical bottleneck in their practical application and paving the way for broader utilization in advanced material applications.

The authors’ work on the CVD synthesis of COF films represents a breakthrough in this regard. By adopting a technique commonly used in semiconductor manufacturing, they have opened up new possibilities for the large-scale production of COFs. This is particularly important considering the growing demand for advanced materials in various industrial sectors. The use of CVD in the synthesis of COF films is a novel approach. The process involves the co-evaporation of two monomers onto a heated substrate, resulting in highly crystalline and defect-free COF films. The precision with which the thickness and crystallinity of these films can be controlled is a significant improvement over previous methods.

The researchers employed a range of sophisticated techniques to characterize the COF films. These included grazing-incidence wide-angle X-ray scattering (GIWAXS), transmission electron microscopy (TEM), Raman spectroscopy, and atomic force microscopy (AFM). Each of these techniques provided insights into the structural integrity, chemical composition, and crystallinity of the COF films, validating the effectiveness of the CVD method. The potential applications of COF films synthesized via CVD are vast. Their high porosity and tunable architecture make them ideal candidates for use in size exclusion membranes, catalytic platforms, and organic transistors. In each of these applications, the properties of COFs can be exploited to achieve higher efficiencies and more effective performance than currently available materials. Moreover, the scalability of the CVD process holds significant industrial implications. The ability to produce large-area COF films quickly and efficiently could lead to the widespread adoption of COFs in various industries, ranging from environmental to electronic sectors.

While the CVD method for synthesizing COF films is promising, it also presents new challenges. For instance, the control of monomer vaporization and deposition parameters is crucial for ensuring the quality of the COF films. There’s a need for further research into optimizing these parameters for different types of COFs. Moreover, exploring the long-term stability and functional durability of these COF films in real-world applications is essential. This would involve subjecting the COF films to various environmental conditions and stressors to ascertain their practical viability.

In summary, the work of Daum et al. in the CVD synthesis of COF films is a landmark achievement in the field of materials science. It addresses a significant challenge in the synthesis of COFs, paving the way for their broader application in various industries. The method they have developed offers a scalable, efficient, and versatile approach to COF film production, which could have far-reaching implications in both industrial and academic sectors. As the field continues to evolve, it will be crucial to build on this foundation, exploring new COF materials and applications that could further revolutionize the material science landscape.

Rapid Synthesis of Crystalline COF Films via Cutting-Edge Chemical Vapor Deposition - Advances in Engineering
Image Credit: ACS Nano, 2023; 17 (21): 21411.

About the author

Rafael Verduzco

Professor and Associate Chair, Chemical & Biomolecular Engineering
Professor, Materials Science & Nanoengineering
Rice University

Rafael Verduzco is a Professor of Chemical and Biomolecular Engineering and Materials Sciences and NanoEngineering at Rice University. He received his Ph.D. in chemical engineering from the California Institute of Technology in 2007 studying liquid crystal polymer gels and his B.S. in chemical engineering from Rice University in 2001. Rafael then went on to a postdoctoral position in the Center for Nanophase Materials Sciences at the Oak Ridge National Laboratory in Tennessee, where he studied bent-core liquid crystals, water-soluble dendrimers for drug delivery, and conjugated polymeric materials for organic electronics.

The Verduzco laboratory uses a combination of polymer chemistry and multi-scale characterization tools to broadly address challenges in polymer science, and current areas of research include polymers for microbial bioelectronics, polymeric membranes for water treatment, and bottlebrush polymer additives for surface modification.


Jeremy P. Daum, Alec Ajnsztajn, Sathvik Ajay Iyengar, Jacob Lowenstein, Soumyabrata Roy, Guan-hui Gao, Esther H. R. Tsai, Pulickel M. Ajayan, Rafael Verduzco. Solutions Are the Problem: Ordered Two-Dimensional Covalent Organic Framework Films by Chemical Vapor Deposition. ACS Nano, 2023; 17 (21): 21411 DOI: 10.1021/acsnano.3c06142

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