journal article·2018-11

High-mobility band-like charge transport in a semiconducting two-dimensional metal–organic framework

Renhao Dong, Peng Han, Himani Arora, Marco Ballabio, Melike Karakus, Zhe Zhang, Chandra Shekhar, Peter Adler, Petko St. Petkov, Artur Erbe, Stefan C. B. Mannsfeld, Claudia Felser, Thomas Heine, Mischa Bonn, Xinliang Feng, Enrique Cánovas

Nature Materials· Volume 17· Issue 11
Publisher page

Abstract

Metal-organic frameworks (MOFs) are hybrid materials based on crystalline coordination polymers that consist of metal ions connected by organic ligands. In addition to the traditional applications in gas storage and separation or catalysis, the long-range crystalline order in MOFs, as well as the tunable coupling between the organic and inorganic constituents, has led to the recent development of electrically conductive MOFs as a new generation of electronic materials. However, to date, the nature of charge transport in the MOFs has remained elusive. Here we demonstrate, using high-frequency terahertz photoconductivity and Hall effect measurements, Drude-type band-like transport in a semiconducting, π-d conjugated porous Fe3(THT)2(NH4)3 (THT, 2,3,6,7,10,11-triphenylenehexathiol) two-dimensional MOF, with a room-temperature mobility up to ~ 220 cm2 V-1 s-1. The temperature-dependent conductivity reveals that this mobility represents a lower limit for the material, as mobility is limited by impurity scattering. These results illustrate the potential for high-mobility semiconducting MOFs as active materials in thin-film optoelectronic devices.
Source: europepmc · Quality: candidate unverified · Source record ↗

Research context

OpenAlex topics: Metal-Organic Frameworks: Synthesis and Applications · Magnetism in coordination complexes · Covalent Organic Framework Applications

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

References (43)

Show source-provided references
1. Li, H., Eddaoudi, M., O’Keeffe, M. & Yaghi, O. M. Design and synthesis of an exceptionally stable and highly porous metal–organic framework. Nature 402, 276–279 (1999).10.1038/46248 ↗
2. Furukawa, H., Cordova, K. E., O’Keeffe, M. & Yaghi, O. M. The chemistry and applications of metal–organic frameworks. Science 341, 1230444 (2013).10.1126/science.1230444 ↗
3. Eddaoudi, M. et al. Systematic design of pore size and functionality in isoreticular MOFs and their application in methane storage. Science 295, 469–472 (2002).10.1126/science.1067208 ↗
4. Murray, L. J., Dincă, M. & Long, J. R. Hydrogen storage in metal–organic frameworks. Chem. Soc. Rev. 38, 1294–1314 (2009).10.1039/b802256a ↗
5. Farha, O. K. et al. De novo synthesis of a metal–organic framework material featuring ultrahigh surface area and gas storage capacities. Nat. Chem. 2, 944–948 (2010).10.1038/nchem.834 ↗
6. McDonald, T. M. et al. Cooperative insertion of CO2 in diamine-appended metal–organic frameworks. Nature 519, 303–308 (2015).10.1038/nature14327 ↗
7. Shimomura, S. et al. Selective sorption of oxygen and nitric oxide by an electron-donating flexible porous coordination polymer. Nat. Chem. 2, 633–637 (2010).10.1038/nchem.684 ↗
8. Li, J. R., Sculley, J. & Zhou, H. C. Metal–organic frameworks for separations. Chem. Rev. 112, 869–932 (2012).10.1021/cr200190s ↗
9. Peng, Y. et al. Metal–organic framework nanosheets as building blocks for molecular sieving membranes. Science 346, 1356–1359 (2014).10.1126/science.1254227 ↗
10. Liao, P., Huang, N., Zhang, W., Zhang, J. & Chen, X. Controlling guest conformation for efficient purification of butadiene. Science 356, 1193–1196 (2017).10.1126/science.aam7232 ↗
11. Lee, J. Y. et al. Metal-organic framework materials as catalysts. Chem. Soc. Rev. 38, 1450–1459 (2009).10.1039/b807080f ↗
12. Zhang, T. & Lin, W. Metal–organic frameworks for artificial photosynthesis and photocatalysis. Chem. Soc. Rev. 43, 5982–5993 (2014).10.1039/C4CS00103F ↗
13. Zhu, L., Liu, X., Jiang, H. & Sun, L. Metal–organic frameworks for heterogeneous basic catalysis. Chem. Rev. 117, 8129–8176 (2017).10.1021/acs.chemrev.7b00091 ↗
14. Talin, A. A. et al. Tunable electrical conductivity in metal–organic framework thin-film devices. Science 343, 66–69 (2014).10.1126/science.1246738 ↗
15. Sun, L., Campbell, M. G. & Dincǎ, M. Electrically conductive porous metal–organic frameworks. Angew. Chem. Int. Ed. 55, 3566–3579 (2016).10.1002/anie.201506219 ↗
16. Stassen, I. et al. An updated roadmap for the integration of metal–organic frameworks with electronic devices and chemical sensors. Chem. Soc. Rev. 46, 3185–3241 (2017).10.1039/C7CS00122C ↗
17. Campbell, M. G., Liu, S. F., Swager, T. M. & Dincă, M. Chemiresistive sensor arrays from conductive 2D metal–organic frameworks. J. Am. Chem. Soc. 137, 13780–13783 (2015).10.1021/jacs.5b09600 ↗
18. Hmadeh, M. et al. New porous crystals of extended metal–catecholates. Chem. Mater. 24, 3511–3513 (2012).10.1021/cm301194a ↗
19. Sheberla, D. et al. High electrical conductivity in Ni3 (2,3,6,7,10,11-hexaiminotriphenylene)2, a semiconducting metal–organic graphene analogue. J. Am. Chem. Soc. 136, 8859–8862 (2014).10.1021/ja502765n ↗
20. Sheberla, D. et al. Conductive MOF electrodes for stable supercapacitors with high areal capacitance. Nat. Mater. 16, 220–224 (2017).10.1038/nmat4766 ↗
21. Kambe, T. et al. π-Conjugated nickel bis(dithiolene) complex nanosheet. J. Am. Chem. Soc. 135, 2462–2465 (2013).10.1021/ja312380b ↗
22. Kambe, T. et al. Redox control and high conductivity of nickel bis(dithiolene) complex π-nanosheet: a potential organic two-dimensional topological insulator. J. Am. Chem. Soc. 136, 14357–14360 (2014).10.1021/ja507619d ↗
23. Huang, X. et al. A two-dimensional π–d conjugated coordination polymer with extremely high electrical conductivity and ambipolar transport behaviour. Nat. Commun. 6, 7408 (2015).10.1038/ncomms8408 ↗
24. Sun, L., Sarah, S., Park, S. S., Dennis Sheberla, D. & Dincă, M. Measuring and reporting electrical conductivity in metal–organic frameworks. J. Am. Chem. Soc. 138, 14772–14782 (2016).10.1021/jacs.6b09345 ↗
25. Clough, A. J. et al. Metallic conductivity in a two-dimensional cobalt dithiolene metal–organic framework. J. Am. Chem. Soc. 139, 10863–10867 (2017).10.1021/jacs.7b05742 ↗
26. Ulbricht, R., Hendry, E., Shan, J., Heinz, T. F. & Bonn, M. Carrier dynamics in semiconductors studied with time-resolved terahertz spectroscopy. Rev. Mod. Phys. 83, 543–586 (2011).10.1103/RevModPhys.83.543 ↗
27. Makiura, R. et al. Surface nano-architecture of a metal–organic framework. Nat. Mater. 9, 565–571 (2010).10.1038/nmat2769 ↗
28. Dong, R. et al. Large-area, free-standing, two-dimensional supramolecular polymer single-layer sheets for highly efficient electrocatalytic hydrogen evolution. Angew. Chem. Int. Ed. 54, 12058–12063 (2015).10.1002/anie.201506048 ↗
29. Lukose, B., Kuc, A. & Heine, T. The structure of layered covalent‐organic frameworks. Chemistry Eur. J. 17, 2388–2392 (2011).10.1002/chem.201001290 ↗
30. Dirk, C. W. et al. Metal poly(benzodithiolenes). Macromolecules 19, 266–269 (1986).10.1021/ma00156a003 ↗
31. Sellmann, D., Geck, M. & Moll, M. Transition-metal complexes with sulfur ligands. 62. Hydrogen evolution upon reaction of protons with sulfur-coordinated iron(ii) complexes. Investigation of the H+, H2, and H– interactions with iron 1,2-benzenedithiolate. J. Am. Chem. Soc. 113, 5259–5264 (1991).10.1021/ja00014a019 ↗
32. Roy, N., Sproules, S., Bill, E., Weyhermüller, T. & Wieghardt, K. Molecular and electronic structure of the square planar bis(o-amidobenzenethiolato)iron(iii) anion and its bis(o-quinoxalinedithiolato)iron(iii) analogue. Inorg. Chem. 47, 10911–10920 (2008).10.1021/ic801109n ↗
33. Darago, L. E., Aubrey, M. L., Yu, C., Gonzalez, M. I. & Long, J. R. Electronic conductivity, ferrimagnetic ordering, and reductive insertion mediated by organic mixed-valence in a ferric semiquinoid metal–organic framework. J. Am. Chem. Soc. 137, 15703–15711 (2015).10.1021/jacs.5b10385 ↗
34. Fonari, A. & Sutton, C. Validation of the effective masses calculated using finite difference method on a five-point stencil for inorganic and organic semiconductors. Preprint at http://arXiv.org/cond-mat.mtrl-sci/1302.4996.
35. Chattopadhyay, D. & Queisser, H. J. Electron scattering by ionized impurities in semiconductors. Rev. Mod. Phys. 53, 745 (1981).10.1103/RevModPhys.53.745 ↗
36. Chen, J. H., Jang, C., Xiao, S., Ishigami, M. & Fuhrer, M. S. Intrinsic and extrinsic performance limits of graphene devices on SiO2. Nat. Nanotech. 3, 206–209 (2008).10.1038/nnano.2008.58 ↗
37. Ma, N. & Jena, D. Charge scattering and mobility in atomically thin semiconductors. Phys. Rev. X 4, 011043 (2014).
38. Radisavljevic, B. & Kis, A. Mobility engineering and a metal–insulator transition in monolayer MoS2. Nat. Mater. 12, 815–820 (2013).10.1038/nmat3687 ↗
39. Kaasbjerg, K., Thygesen, K. S. & Jacobsen, K. W. Phonon-limited mobility in n-type single-layer MoS2 from first principles. Phys. Rev. B 85, 115317 (2012).10.1103/PhysRevB.85.115317 ↗
40. Sun, L. et al. Is iron unique in promoting electrical conductivity in MOFs? Chem. Sci. 8, 4450–4457 (2017).10.1039/C7SC00647K ↗
41. Mayadas, F. & Shatzkes, M. Electrical-resistivity model for polycrystalline films: the case of arbitrary reflection at external surfaces. Phys. Rev. B 1, 1382–1389 (1970).10.1103/PhysRevB.1.1382 ↗
42. Rivnay, J. et al. Large modulation of carrier transport by grain-boundary molecular packing and microstructure in organic thin films. Nat. Mater. 8, 952–958 (2009).10.1038/nmat2570 ↗
43. Steinhauser, J., Fay, S., Oliveira, N., Vallat-Sauvain, E. & Ballif, C. Transition between grain boundary and intragrain scattering transport mechanisms in boron-doped zinc oxide thin films. Appl. Phys. Lett. 90, 142107 (2007).10.1063/1.2719158 ↗