A semiconducting molecular ferroelectric with a bandgap much lower than that of BiFeO3
Source abstract
Abstract
Ferroelectrics have been attracting increasing attention as good candidates for multifunctional materials because of their fascinating properties. However, their large bandgap has been a roadblock limiting their application in optoelectronics and photovoltaics, among other applications. Hybrid ferroelectrics have the potential to combine the advantages of both molecular materials and ferroelectrics. In this context, we designed a hybrid ferroelectric: (2-(ammoniomethyl)pyridinium)SbI5. It shows an above-room-temperature Curie temperature (Tc=360 K), a large spontaneous polarization (Ps=4 μC cm−2) and a small bandgap (2.03 eV) that is much smaller than the recently reported 2.7–3.65 eV for the lead-halide perovskite ferroelectrics. The implementation of ferroelectricity in hybrid semiconducting materials may be a feasible way to realize high-performance ferroelectric optoelectronic and photovoltaic devices. Replacing lead-based perovskite crystals with hybrid organic–inorganic materials may generate safer, more efficient solar cell devices. Lead halide perovskites can convert over 20% of incoming light to electricity and are inexpensive to produce, but have troubling moisture instability and toxicity issues. Ren-Gen Xiong from China's Southeast University and colleagues investigated alternatives based on semiconducting ferroelectrics that offer polarization-based manipulation of photogenerated electrons. Because all-inorganic ferroelectrics typically have poor light sensitivity due to their large bandgaps, the researchers synthesized a new compound that fuses antimony and iodine atoms with organonitrogen rings. These large, dark-red crystals show room-temperature ferroelectricity that can be manipulated at nanoscale dimensions using force microscopy. Furthermore, tweaking the antimony–iodine framework with the organic component lowered the bandgap to levels even below those of lead halides. A semiconducting molecular ferroelectric (2-(ammoniomethyl)pyridinium)SbI5 was designed. It shows an above-room-temperature Curie temperature (Tc=360 K), a large spontaneous polarization (Ps=4 μC cm−2) and small bandgap (2.03 eV) that are comparable to those of the well-known semiconducting ferroelectrics BiFeO3 (Eg=2.7 eV) and SbSI (Eg=2.0 eV). The implementation of ferroelectricity into hybrid semiconducting materials will move the applications of hybrid semiconducting molecular ferroelectrics in optoelectronic and photovoltaics devices forward.
Source: openalex_inverted_index · Quality: baseline
Research context
OpenAlex topics: Perovskite Materials and Applications · Solid-state spectroscopy and crystallography · Conducting polymers and applications
SciVX discovery tags are terminology-based. OpenAlex topics are source-provided classifications.
References (45)
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1. Yang, W. S., Noh, J. H., Jeon, N. J., Kim, Y. C., Ryu, S., Seo, J. & Seok, S. I. High-performance photovoltaic perovskite layers fabricated through intramolecular exchange. Science 348, 1234–1237 (2015).10.1126/science.aaa9272 ↗
2. Jeon, N. J., Noh, J. H., Yang, W. S., Kim, Y. C., Ryu, S., Seo, J. & Seok, S. I. Compositional engineering of perovskite materials for high-performance solar cells. Nature 517, 476–480 (2015).10.1038/nature14133 ↗
3. Pellet, N., Gao, P., Gregori, G., Yang, T. Y., Nazeeruddin, M. K., Maier, J. & Gratzel, M. Mixed-organic-cation perovskite photovoltaics for enhanced solar-light harvesting. Angew. Chem. Int. Ed. 53, 3151–3157 (2014).10.1002/anie.201309361 ↗
4. Yang, B., Dyck, O., Poplawsky, J., Keum, J., Das, S., Puretzky, A., Aytug, T., Joshi, P. C., Rouleau, C. M., Duscher, G., Geohegan, D. B. & Xiao, K. Controllable growth of perovskite films by room-temperature air exposure for efficient planar heterojunction photovoltaic cells. Angew. Chem. Int. Ed. 54, 14862–14865 (2015).10.1002/anie.201505882 ↗
5. Zhou, Z., Wang, Z., Zhou, Y., Pang, S., Wang, D., Xu, H., Liu, Z., Padture, N. P. & Cui, G. Methylamine-gas-induced defect-healing behavior of ch3nh3pbi3 thin films for perovskite solar cells. Angew. Chem. Int. Ed. 54, 9705–9709 (2015).10.1002/anie.201504379 ↗
6. Green, M. A. & Bein, T. Photovoltaics perovskite cells charge forward. Nat. Mater. 14, 559–561 (2015).10.1038/nmat4301 ↗
7. Hao, F., Stoumpos, C. C., Cao, D. H., Chang, R. P. H. & Kanatzidis, M. G. Lead-free solid-state organic–inorganic halide perovskite solar cells. Nat. Photonics 8, 489–494 (2014).10.1038/nphoton.2014.82 ↗
8. Hao, F., Stoumpos, C. C., Guo, P. J., Zhou, N. J., Marks, T. J., Chang, R. P. H. & Kanatzidis, M. G. Solvent-mediated crystallization of CH3NH3SnI3 films for heterojunction depleted perovskite solar cells. J. Am. Chem. Soc. 137, 11445–11452 (2015).10.1021/jacs.5b06658 ↗
9. Choi, T., Lee, S., Choi, Y. J., Kiryukhin, V. & Cheong, S. W. Switchable ferroelectric diode and photovoltaic effect in BiFeO3 . Science 324, 63–66 (2009).10.1126/science.1168636 ↗
10. Grinberg, I., West, D. V., Torres, M., Gou, G. Y., Stein, D. M., Wu, L. Y., Chen, G. N., Gallo, E. M., Akbashev, A. R., Davies, P. K., Spanier, J. E. & Rappe, A. M. Perovskite oxides for visible-light-absorbing ferroelectric and photovoltaic materials. Nature 503, 509–512 (2013).10.1038/nature12622 ↗
11. Yang, S. Y., Seidel, J., Byrnes, S. J., Shafer, P., Yang, C. H., Rossell, M. D., Yu, P., Chu, Y. H., Scott, J. F., Ager, J. W. III, Martin, L. W. & Ramesh, R. Above-bandgap voltages from ferroelectric photovoltaic devices. Nat. Nanotechnol. 5, 143–147 (2010).10.1038/nnano.2009.451 ↗
12. Ho Sung, J., Lee, W.-M., Hong Lee, J., Chu, K., Lee, D., Moya, X., Mathur, N. D., Yang, C.-H., Park, J.-H. & Jo, M.-H. Single ferroelectric-domain photovoltaic switch based on lateral BiFeO3 cells. NPG Asia Mater. 5, e189 (2013).10.1038/am.2013.1 ↗
13. Ye, H. Y., Liao, W. Q., Hu, C. L., Zhang, Y., You, Y. M., Mao, J. G., Li, P. F. & Xiong, R. G. Bandgap engineering of lead-halide perovskite-type ferroelectrics. Adv. Mater. 28, 2579–2586 (2016).10.1002/adma.201505224 ↗
14. Liao, W. Q., Zhang, Y., Hu, C. L., Mao, J. G., Ye, H.-Y., Li, P. F., Huang, S. D. & Xiong, R.-G. A lead-halide perovskite molecular ferroelectric semiconductor. Nat. Commun. 6, 7338 (2015).10.1038/ncomms8338 ↗
15. Park, B. W., Philippe, B., Zhang, X., Rensmo, H., Boschloo, G. & Johansson, E. M. Bismuth based hybrid perovskites A3Bi2I9 (A: Methylammonium or cesium) for solar cell application. Adv. Mater. 27, 6808–6813 (2015).
16. Saparov, B., Hong, F., Sun, J. P., Duan, H. S., Meng, W. W., Cameron, S., Hill, I. G., Yan, Y. F. & Mitzi, D. B. Thin-film preparation and characterization of Cs3Sb2I9: a lead-free layered perovskite semiconductor. Chem. Mater. 27, 5622–5632 (2015).10.1021/acs.chemmater.5b01989 ↗
17. Ye, H.-Y., Li, S. H., Zhang, Y., Zhou, L., Deng, F. & Xiong, R.-G. Solid state molecular dynamic investigation of an inclusion ferroelectric: [(2,6-diisopropylanilinium)([18]crown-6)]BF4 . J. Am. Chem. Soc. 136, 10033–10040 (2014).10.1021/ja503344b ↗
18. Ye, H.-Y., Zhang, Y., Fu, D. W. & Xiong, R.-G. A displacive-type metal crown ether ferroelectric compound: Ca(NO3 2(15-crown-5). Angew. Chem. Int. Ed. 53, 6724–6729 (2014).10.1002/anie.201402339 ↗
19. Segall, M. D., Lindan, P. J. D., Probert, M. J., Pickard, C. J., Hasnip, P. J., Clark, S. J. & Payne, M. C. First-principles simulation: ideas, illustrations and the CASTEP code. J. Phys. Condens. Matter 14, 2717–2744 (2002).10.1088/0953-8984/14/11/301 ↗
20. Perdew, J. P., Burke, K. & Ernzerhof, M. Generalized gradient approximation made simple. Phys. Rev. Lett. 77, 3865–3868 (1996).10.1103/PhysRevLett.77.3865 ↗
21. Mercier, N., Louvain, N. & Bi, W. H. Structural diversity and retro-crystal engineering analysis of iodometalate hybrids. CrystEngComm. 11, 720–734 (2009).10.1039/b817891g ↗
22. Mitzi, D. B. Synthesis, structure, and properties of organic-inorganic perovskites and related materials. Prog. Inorg. Chem. 48, 1–121 (1999).
23. Saparov, B. & Mitzi, D. B. Organic-inorganic perovskites: structural versatility for functional materials design. Chem. Rev. 116, 4558–4596 (2016).10.1021/acs.chemrev.5b00715 ↗
24. Mitzi, D. B., Feild, C. A., Harrison, W. T. A. & Guloy, A. M. Conducting tin halides with a layered organic-based perovskite structure. Nature 369, 467–469 (1994).10.1038/369467a0 ↗
25. Kagan, C. R., Mitzi, D. B. & Dimitrakopoulos, C. D. Organic-inorganic hybrid materials as semiconducting channels in thin-film field-effect transistors. Science 286, 945–947 (1999).10.1126/science.286.5441.945 ↗
26. Ishi, J., Kunugita, H., Ema, K., Ban, T. & Kondo, T. Time-to-space conversion of Tbits/s optical pulses using a self-organized quantum-well material. Appl. Phys. Lett. 77, 3487–3489 (2000).10.1063/1.1328365 ↗
27. Stranks, S. D., Eperon, G. E., Grancini, G., Menelaou, C., Alcocer, M. J. P., Leijtens, T., Herz, L. M., Petrozza, A. & Snaith, H. J. Electron-hole diffusion lengths exceeding 1 micrometer in an organometal trihalide perovskite absorber. Science 342, 341–344 (2013).10.1126/science.1243982 ↗
28. Wehrenfennig, C., Eperon, G. E., Johnston, M. B., Snaith, H. J. & Herz, L. M. High charge carrier mobilities and lifetimes in organolead trihalide perovskites. Adv. Mater. 26, 1584–1589 (2014).10.1002/adma.201305172 ↗
29. Lines, M. E. & Glass, A. M. Principles and Applications of Ferroelectrics and Related Materials, (Clarendon Press: Oxford, 1977).
30. Poglitsch, A. & Weber, D. Dynamic disorder in methylammoniumtrihalogenoplumbates (II) observed by millimeter-wave spectroscopy. J. Chem. Phys. 87, 6373 (1987).10.1063/1.453467 ↗
31. Stoumpos, C. C., Malliakas, C. D. & Kanatzidis, M. G. Semiconducting tin and lead iodide perovskites with organic cations: phase transitions, high mobilities, and near-infrared photoluminescent properties. Inorg. Chem. 52, 9019–9038 (2013).10.1021/ic401215x ↗
32. Yang, T. Y., Gregori, G., Pellet, N., Gratzel, M. & Maier, J. The significance of ion conduction in a hybrid organic-inorganic lead-iodide-based perovskite photosensitizer. Angew. Chem. Int. Ed. 54, 7905–7910 (2015).10.1002/anie.201500014 ↗
33. Zhang, W., Cai, Y., Xiong, R.-G., Yoshikawa, H. & Awaga, K. Exceptional dielectric phase transitions in a perovskite-type cage compound. Angew. Chem. Int. Ed. 49, 6608–6610 (2010).10.1002/anie.201001208 ↗
34. Sawyer, C. & Tower, C. Rochelle salt as a dielectric. Phys. Rev. 35, 269–273 (1930).10.1103/PhysRev.35.269 ↗
35. Zhang, W. & Xiong, R.-G. Ferroelectric metal-organic frameworks. Chem. Rev. 112, 1163–1195 (2012).10.1021/cr200174w ↗
36. Xu, G. C., Zhang, W., Ma, X. M., Chen, Y. H., Zhang, L., Cai, H. L., Wang, Z. M., Xiong, R.-G. & Gao, S. Coexistence of magnetic and electric orderings in the metal-formate frameworks of [NH4][M(HCOO)3]. J. Am. Chem. Soc. 133, 14948–14951 (2011).10.1021/ja206891q ↗
37. Ye, H.-Y., Zhang, Y., Fu, D.-W. & Xiong, R.-G. An above-room-temperature ferroelectric organo-metal halide perovskite: (3-pyrrolinium)(CdCl3 . Angew. Chem. Int. Ed. 53, 11242–11247 (2014).10.1002/anie.201406810 ↗
38. Sun, Z., Liu, X., Khan, T., Ji, C., Asghar, M. A., Zhao, S., Li, L., Hong, M. & Luo, J. A photoferroelectric perovskite-type organometallic halide with exceptional anisotropy of bulk photovoltaic effects. Angew. Chem. Int. Ed. 55, 6545–6550 (2016).10.1002/anie.201601933 ↗
39. Fu, D. W., Zhang, W., Cai, H. L., Zhang, Y., Ge, J. Z., Xiong, R.-G., Huang, S. D. & Nakamura, T. A multiferroic perdeutero metal-organic framework. Angew. Chem. Int. Ed. 50, 11947–11951 (2011).10.1002/anie.201103265 ↗
40. Li, X. L., Chen, K., Liu, Y., Wang, Z. X., Wang, T. W., Zuo, J. L., Li, Y. Z., Wang, Y., Zhu, J. S., Liu, J. M., Song, Y. & You, X. Z. Molecule-based ferroelectric thin films: mononuclear lanthanide enantiomers displaying room-temperature ferroelectric and dielectric properties. Angew. Chem. Int. Ed. 46, 6820–6823 (2007).10.1002/anie.200701802 ↗
41. Gao, W., Chang, L., Ma, H., You, L., Yin, J., Liu, J., Liu, Z., Wang, J. & Yuan, G. Flexible organic ferroelectric films with a large piezoelectric response. NPG Asia Mater. 7, e189 (2015).10.1038/am.2015.54 ↗
42. Fukunaga, M. & Noda, Y. New technique for measuring ferroelectric and antiferroelectric hysteresis loops. J. Phys. Soc. Jpn 77, 064706 (2008).10.1143/JPSJ.77.064706 ↗
43. Tauc, J., Grigorov, R & Vancu, A. Optical properties and electronic structure of amorphous germanium. Phys. Stat. Sol. (b) 15, 627–637 (1966).10.1002/pssb.19660150224 ↗
44. Cao, D. H., Stoumpos, C. C., Farha, O. K., Hupp, J. T. & Kanatzidis, M. G. 2D homologous perovskites as light-absorbing materials for solar cell applications. J. Am. Chem. Soc. 137, 7843–7850 (2015).10.1021/jacs.5b03796 ↗
45. Smith, I. C., Hoke, E. T., Solis-Ibarra, D., McGehee, M. D. & Karunadasa, H. I. A layered hybrid perovskite solar-cell absorber with enhanced moisture stability. Angew. Chem. Int. Ed. 53, 11232–11235 (2014).10.1002/anie.201406466 ↗