TY - JOUR
T1 - Crystallizing Sub 10 nm Covalent Organic Framework Thin Films via Interfacial-Residual Concomitance
AU - Kumar Mahato, Ashok
AU - Bag, Saikat
AU - Sasmal, Himadri Sekhar
AU - Dey, Kaushik
AU - Giri, Indrajit
AU - Linares-Moreau, Mercedes
AU - Carbonell, Carlos
AU - Falcaro, Paolo
AU - Gowd, E. Bhoje
AU - Vijayaraghavan, Ratheesh K.
AU - Banerjee, Rahul
N1 - Funding Information:
A.K.M. and S.B. acknowledge CSIR for a research fellowship. K.D. acknowledges DST-SERB, India, for an RA fellowship [CRG/2018/000314]. R.B. acknowledges a SwarnaJayanti Fellowship grant [DST/SJF/CSA-02/2016-2017], DST Mission Innovation [DST/TM/EWO/MI/CCUS/17 and DST/TMD(EWO)/IC5-2018/01(C)], and DST SERB [CRG/2018/000314] for funding. M.L.-M., C.C.C., and P.F. acknowledge the European Union’s Horizon 2020 Program (FP/2104-2020)/ERC Grant Agreement No. 771834 POPCRYSTAL and Anton Paar. The authors acknowledge the use of the Somapp Lab, a core facility supported by the Austrian Federal Ministry of Education, Science and Research, TU Graz, UNI Graz, and Anton Paar GmbH. We acknowledge Mr. H. Shebeeb Kunjattu for the contact angle data collection and Mr. R. B. Amal Raj for helping with PXRD data collection. We thank Prof. Rajesh Kumar and Ms. Manushree Tanwar for the Raman data collection. R.B. acknowledges Carl Friedrich von Siemens Research Fellowship and the Alexander von Humboldt Foundation.
Publisher Copyright:
©
PY - 2021/12/15
Y1 - 2021/12/15
N2 - Synthesis of covalent organic framework (COF) thin films on different supports with high crystallinity and porosity is crucial for their potential applications. We have designed a new synchronized methodology, residual crystallization (RC), to synthesize sub 10 nm COF thin films. These residual crystallized COF thin films showcase high surface area, crystallinity, and conductivity at room temperature. We have used interfacial crystallization (IC) as a rate-controlling tool for simultaneous residual crystallization. We have also diversified the methodology of residual crystallization by utilizing two different crystallization pathways: fiber-to-film (F-F) and sphere-to-film (S-F). In both cases, we could obtain continuous COF thin films with high crystallinity and porosity grown on various substrates (the highest surface area of a TpAzo COF thin film being 2093 m2 g-1). Precise control over the crystallization allows the synthesis of macroscopic defect-free sub 10 nm COF thin films with a minimum thickness of ∼1.8 nm. We have synthesized two COF thin films (TpAzo and TpDPP) using F-F and S-F pathways on different supports such as borosilicate glass, FTO, silicon, Cu, metal, and ITO. Also, we have investigated the mechanism of the growth of these thin films on various substrates with different wettability. Further, a hydrophilic support (glass) was used to grow the thin films in situ for four-probe system device fabrication. All residual crystallized COF thin films exhibit outstanding conductivity values. We could obtain a conductivity of 3.7 × 10-2 mS cm-1 for the TpAzo film synthesized by S-F residual crystallization.
AB - Synthesis of covalent organic framework (COF) thin films on different supports with high crystallinity and porosity is crucial for their potential applications. We have designed a new synchronized methodology, residual crystallization (RC), to synthesize sub 10 nm COF thin films. These residual crystallized COF thin films showcase high surface area, crystallinity, and conductivity at room temperature. We have used interfacial crystallization (IC) as a rate-controlling tool for simultaneous residual crystallization. We have also diversified the methodology of residual crystallization by utilizing two different crystallization pathways: fiber-to-film (F-F) and sphere-to-film (S-F). In both cases, we could obtain continuous COF thin films with high crystallinity and porosity grown on various substrates (the highest surface area of a TpAzo COF thin film being 2093 m2 g-1). Precise control over the crystallization allows the synthesis of macroscopic defect-free sub 10 nm COF thin films with a minimum thickness of ∼1.8 nm. We have synthesized two COF thin films (TpAzo and TpDPP) using F-F and S-F pathways on different supports such as borosilicate glass, FTO, silicon, Cu, metal, and ITO. Also, we have investigated the mechanism of the growth of these thin films on various substrates with different wettability. Further, a hydrophilic support (glass) was used to grow the thin films in situ for four-probe system device fabrication. All residual crystallized COF thin films exhibit outstanding conductivity values. We could obtain a conductivity of 3.7 × 10-2 mS cm-1 for the TpAzo film synthesized by S-F residual crystallization.
UR - http://www.scopus.com/inward/record.url?scp=85120892612&partnerID=8YFLogxK
U2 - 10.1021/jacs.1c09740
DO - 10.1021/jacs.1c09740
M3 - Article
C2 - 34855393
AN - SCOPUS:85120892612
SN - 0002-7863
VL - 143
SP - 20916
EP - 20926
JO - Journal of the American Chemical Society
JF - Journal of the American Chemical Society
IS - 49
ER -