journal article·2021-08Open access

Thermally conductive ultra-low-k dielectric layers based on two-dimensional covalent organic frameworks

Austin M. Evans, Ashutosh Giri, Vinod K. Sangwan, Sangni Xun, Matthew Bartnof, Carlos G. Torres-Castanedo, Halleh B. Balch, Matthew S. Rahn, Nathan P. Bradshaw, Edon Vitaku, David W. Burke, Hong Li, Michael J. Bedzyk, Feng Wang, Jean-Luc Brédas, Jonathan A. Malen, Alan J. H. McGaughey, Mark C. Hersam, William R. Dichtel, Patrick E. Hopkins

Nature Materials· Volume 20· Issue 8

Abstract

As the features of microprocessors are miniaturized, low-dielectric-constant (low-k) materials are necessary to limit electronic crosstalk, charge build-up, and signal propagation delay. However, all known low-k dielectrics exhibit low thermal conductivities, which complicate heat dissipation in high-power-density chips. Two-dimensional (2D) covalent organic frameworks (COFs) combine immense permanent porosities, which lead to low dielectric permittivities, and periodic layered structures, which grant relatively high thermal conductivities. However, conventional synthetic routes produce 2D COFs that are unsuitable for the evaluation of these properties and integration into devices. Here, we report the fabrication of high-quality COF thin films, which enable thermoreflectance and impedance spectroscopy measurements. These measurements reveal that 2D COFs have high thermal conductivities (1 W m-1 K-1) with ultra-low dielectric permittivities (k = 1.6). These results show that oriented, layered 2D polymers are promising next-generation dielectric layers and that these molecularly precise materials offer tunable combinations of useful properties.
Source: europepmc · Quality: candidate unverified · Source record ↗

Research context

OpenAlex topics: Thermal properties of materials · Graphene research and applications · Synthesis and properties of polymers

SciVX discovery tags are terminology-based. OpenAlex topics are source-provided classifications.

References (40)

Show source-provided references
1. Krishtab, M. et al. Vapor-deposited zeolitic imidazolate frameworks as gap-filling ultra-low-k dielectrics. Nat. Commun. 10, 3729 (2019).10.1038/s41467-019-11703-x ↗
2. Volksen, W., Miller, R. D. & Dubois, G. Low dielectric constant materials. Chem. Rev. 110, 56–110 (2010).10.1021/cr9002819 ↗
3. Maex, K. et al. Low dielectric constant materials for microelectronics. J. Appl. Phys. 93, 8793–8841 (2003).10.1063/1.1567460 ↗
4. International Roadmap for Devices and Systems (IRDS) (IEEE, 2017); https://irds.ieee.org/
5. Arden, W. M. The international technology roadmap for semiconductors—perspectives and challenges for the next 15 years. Curr. Opin. Solid State Mater. Sci. 6, 371–377 (2002).10.1016/S1359-0286(02)00116-X ↗
6. Miller, R. D. In search of low-k dielectrics. Science 286, 421–423 (1999).10.1126/science.286.5439.421 ↗
7. Veres, J., Ogier, S. D., Leeming, S. W., Cupertino, D. C. & Mohialdin Khaffaf, S. Low-k insulators as the choice of dielectrics in organic field-effect transistors. Adv. Func. Mater. 13, 199–204 (2003).10.1002/adfm.200390030 ↗
8. Hopkins, P. E., Kaehr, B., Piekos, E. S., Dunphy, D. & Brinker, C. J. Minimum thermal conductivity considerations in aerogel thin films. J. Appl. Phys. 111, 113532 (2012).10.1063/1.4729325 ↗
9. Erickson, K. J. et al. Thin film thermoelectric metal–organic framework with high Seebeck coefficient and low thermal conductivity. Adv. Mater. 27, 3453–3459 (2015).10.1002/adma.201501078 ↗
10. Xie, X. et al. Thermal conductivity, heat capacity, and elastic constants of water-soluble polymers and polymer blends. Macromolecules 49, 972–978 (2016).10.1021/acs.macromol.5b02477 ↗
11. Kim, G.-H. et al. High thermal conductivity in amorphous polymer blends by engineered interchain interactions. Nat. Mater. 14, 295–300 (2015).10.1038/nmat4141 ↗
12. Evans, A. M. et al. Buckling of two-dimensional covalent organic frameworks under thermal stress. Ind. Eng. Chem. Res. 58, 9883–9887 (2019).10.1021/acs.iecr.9b01288 ↗
13. Bisbey, R. P. & Dichtel, W. R. Covalent organic frameworks as a platform for multidimensional polymerization. ACS Cent. Sci. 3, 533–543 (2017).10.1021/acscentsci.7b00127 ↗
14. Sick, T. et al. Oriented films of conjugated 2D covalent organic frameworks as photocathodes for water splitting. J. Am. Chem. Soc. 140, 2085–2092 (2018).10.1021/jacs.7b06081 ↗
15. Colson, J. W. et al. Oriented 2D covalent organic framework thin films on single-layer graphene. Science 332, 228–231 (2011).10.1126/science.1202747 ↗
16. Burke, D. W. et al. Acid exfoliation of imine-linked covalent organic frameworks enables solution processing into crystalline thin films. Angew. Chem. Int. Ed. 59, 5165–5171 (2019).10.1002/anie.201913975 ↗
17. Chen, X. et al. High-lithium-affinity chemically exfoliated 2D covalent organic frameworks. Adv. Mater. 31, 1901640 (2019).10.1002/adma.201901640 ↗
18. Dey, K. et al. Selective molecular separation by interfacially crystallized covalent organic framework thin films. J. Am. Chem. Soc. 139, 13083–13091 (2017).10.1021/jacs.7b06640 ↗
19. Sasmal, H. S. et al. Covalent self-assembly in two dimensions: connecting covalent organic framework nanospheres into crystalline and porous thin films. J. Am. Chem. Soc. 141, 20371–20379 (2019).10.1021/jacs.9b10788 ↗
20. Rodríguez-San-Miguel, D. & Zamora, F. Processing of covalent organic frameworks: an ingredient for a material to succeed. Chem. Soc. Rev. 48, 4375–4386 (2019).10.1039/C9CS00258H ↗
21. Shao, P. et al. Flexible films of covalent organic frameworks with ultralow dielectric constants under high humidity. Angew. Chem. Int. Ed. 57, 16501–16505 (2018).10.1002/anie.201811250 ↗
22. Evans, A. M. et al. Seeded growth of single-crystal two-dimensional covalent organic frameworks. Science 361, 52–57 (2018).10.1126/science.aar7883 ↗
23. Li, H. et al. Nucleation–elongation dynamics of two-dimensional covalent organic frameworks. J. Am. Chem. Soc. 142, 1367–1374 (2020).10.1021/jacs.9b10869 ↗
24. Smith, B. J. et al. Colloidal covalent organic frameworks. ACS Cent. Sci. 3, 58–65 (2017).10.1021/acscentsci.6b00331 ↗
25. Cao, S., Li, B., Zhu, R. & Pang, H. Design and synthesis of covalent organic frameworks towards energy and environment fields. Chem. Eng. J. 355, 602–623 (2019).10.1016/j.cej.2018.08.184 ↗
26. Ikeda, M., Takeuchi, M. & Shinkai, S. Unusual emission properties of a triphenylene-based organogel system. Chem. Commun. 9, 1354–1355 (2003).10.1039/b302415f ↗
27. Sangwan, V. K. et al. Quantitatively enhanced reliability and uniformity of high-κ dielectrics on graphene enabled by self-assembled seeding layers. Nano Lett. 13, 1162–1167 (2013).10.1021/nl3045553 ↗
28. Huang, B. L., McGaughey, A. J. H. & Kaviany, M. Thermal conductivity of metal-organic framework 5 (MOF-5): Part I. Molecular dynamics simulations. Int. J. Heat Mass Transf. 50, 393–404 (2007).10.1016/j.ijheatmasstransfer.2006.10.002 ↗
29. Wang, X., Liman, C. D., Treat, N. D., Chabinyc, M. L. & Cahill, D. G. Ultralow thermal conductivity of fullerene derivatives. Phys. Rev. B 88, 075310 (2013).10.1103/PhysRevB.88.075310 ↗
30. Klemens, P. G. The scattering of low-frequency lattice waves by static imperfections. Proc. Phys. Soc. A 68, 1113 (1955).10.1088/0370-1298/68/12/303 ↗
31. Gaskins, J. T. et al. Investigation and review of the thermal, mechanical, electrical, optical, and structural properties of atomic layer deposited high-k dielectrics: beryllium oxide, aluminum oxide, hafnium oxide, and aluminum nitride. ECS J. Solid State Sci. Technol. 6, N189 (2017).10.1149/2.0091710jss ↗
32. Scott, E. A., Gaskins, J. T., King, S. W. & Hopkins, P. E. Thermal conductivity and thermal boundary resistance of atomic layer deposited high-k dielectric aluminum oxide, hafnium oxide, and titanium oxide thin films on silicon. APL Mater. 6, 058302 (2018).10.1063/1.5021044 ↗
33. Giri, A., Tomko, J., Gaskins, J. T. & Hopkins, P. E. Large tunability in the mechanical and thermal properties of carbon nanotube-fullerene hierarchical monoliths. Nanoscale 10, 22166–22172 (2018).10.1039/C8NR06848H ↗
34. McGaughey, A. J. H. & Kaviany, M. Thermal conductivity decomposition and analysis using molecular dynamics simulations: Part II. Complex silica structures. Int. J. Heat Mass Transf. 47, 1799–1816 (2004).10.1016/j.ijheatmasstransfer.2003.11.009 ↗
35. Jiang, Z. GIXSGUI: a MATLAB toolbox for grazing-incidence X-ray scattering data visualization and reduction, and indexing of buried three-dimensional periodic nanostructured films. J. Appl. Crystallogr. 48, 917–926 (2015).10.1107/S1600576715004434 ↗
36. Gajdoš, M., Hummer, K., Kresse, G., Furthmüller, J. & Bechstedt, F. Linear optical properties in the projector-augmented wave methodology. Phys. Rev. B 73, 045112 (2006).10.1103/PhysRevB.73.045112 ↗
37. Perdew, J. P., Burke, K. & Ernzerhof, M. Generalized gradient approximation made simple. Phys. Rev. Lett. 77, 3865–3868 (1996).10.1103/PhysRevLett.77.3865 ↗
38. Plimpton, S. Fast parallel algorithms for short-range molecular dynamics. J. Comput. Phys. 117, 1–19 (1995).10.1006/jcph.1995.1039 ↗
39. Stuart, S. J., Tutein, A. B. & Harrison, J. A. A reactive potential for hydrocarbons with intermolecular interactions. J. Chem. Phys. 112, 6472–6486 (2000).10.1063/1.481208 ↗
40. Hoover, W. G. & Posch, H. A. Direct measurement of Lyapunov exponents. Phys. Lett. A 113, 82–84 (1985).10.1016/0375-9601(85)90659-0 ↗