Molecular engineering of organic–inorganic hybrid perovskites quantum wells

Abstract

Semiconductor quantum-well structures and superlattices are key building blocks in modern optoelectronics, but it is difficult to simultaneously realize defect-free epitaxial growth while fine tuning the chemical composition, layer thickness and band structure of each layer to achieve the desired performance. Here we demonstrate the modulation of the electronic structure—and consequently the optical properties—of organic semiconducting building blocks that are incorporated between the layers of perovskites through a facile solution processing step. Self-aggregation of the conjugated organic molecules is suppressed by functionalization with sterically demanding groups and single crystalline organic–perovskite hybrid quantum wells (down to one-unit-cell thick) are obtained. The energy and charge transfers between adjacent organic and inorganic layers are shown to be fast and efficient, owing to the atomically flat interface and ultrasmall interlayer distance of the perovskite materials. The resulting two-dimensional hybrid perovskites are very stable due to protection given by the bulky hydrophobic organic groups.

Access options

Rent or Buy article

Get time limited or full article access on ReadCube.

from$8.99

All prices are NET prices.

Fig. 1: The structures of the conjugated organic ligands and 2D hybrid perovskites.
Fig. 2: Optical properties of the hybrid halide perovskites quantum wells.
Fig. 3: Time- and spectral-resolved PL spectroscopy.
Fig. 4: Stability of hybrid halide perovskite quantum wells.

Data availability

Crystallographic data for the structures reported in this Article have been deposited at the Cambridge Crystallographic Data Centre under deposition numbers CCDC 1846391 [(4Tm)2PbI4], 1846392 [(BTm)2PbI4] and 1861843 [(2T)2PbI4]. Copies of the data can be obtained free of charge through https://www.ccdc.cam.ac.uk/structures/. All other data supporting the findings of this study are available within the Article and its Supplementary Information or from the corresponding author on reasonable request.

Change history

  • 20 July 2020

    An amendment to this paper has been published and can be accessed via a link at the top of the paper.

References

  1. 1.

    Levine, B. F. Quantum-well infrared photodetectors. J. Appl. Phys. 74, R1–R81 (1993).

    CAS  Google Scholar 

  2. 2.

    Shuji, N. et al. InGaN-based multi-quantum-well-structure laser diodes. Jpn. J. Appl. Phys. 35, L74 (1996).

    Google Scholar 

  3. 3.

    Hicks, L. D. & Dresselhaus, M. S. Effect of quantum-well structures on the thermoelectric figure of merit. Phys. Rev. B 47, 12727–12731 (1993).

    CAS  Google Scholar 

  4. 4.

    Ishihara, T., Takahashi, J. & Goto, T. Exciton state in two-dimensional perovskite semiconductor (C10H21NH3)2PbI4. Solid State Commun. 69, 933–936 (1989).

    CAS  Google Scholar 

  5. 5.

    Meresse, A. & Daoud, A. Bis(n-propylammonium) tetrachloroplumbate. Acta Crystallogr. C 45, 194–196 (1989).

    Google Scholar 

  6. 6.

    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).

    Google Scholar 

  7. 7.

    Mitzi, D. B., Wang, S., Feild, C. A., Chess, C. A. & Guloy, A. M. Conducting layered organic-inorganic halides containing <110>-oriented perovskite sheets. Science 267, 1473–1476 (1995).

    CAS  PubMed  Google Scholar 

  8. 8.

    Papavassiliou, G. C. Three- and low-dimensional inorganic semiconductors. Prog. Solid State Chem. 25, 125–270 (1997).

    CAS  Google Scholar 

  9. 9.

    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).

    CAS  PubMed  Google Scholar 

  10. 10.

    Borriello, I., Cantele, G. & Ninno, D. Ab initio investigation of hybrid organic-inorganic perovskites based on tin halides. Phys. Rev. B 77, 235214 (2008).

    Google Scholar 

  11. 11.

    Lanty, G. et al. Room-temperature optical tunability and inhomogeneous broadening in 2D-layered organic–inorganic perovskite pseudobinary alloys. J. Phys. Chem. Lett. 5, 3958–3963 (2014).

    CAS  PubMed  Google Scholar 

  12. 12.

    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).

    CAS  Google Scholar 

  13. 13.

    Dou, L. T. et al. Atomically thin two-dimensional organic-inorganic hybrid perovskites. Science 349, 1518–1521 (2015).

    CAS  PubMed  Google Scholar 

  14. 14.

    Ha, S. T., Shen, C., Zhang, J. & Xiong, Q. H. Laser cooling of organic-inorganic lead halide perovskites. Nat. Photon. 10, 115–121 (2016).

    CAS  Google Scholar 

  15. 15.

    Stoumpos, C. C. et al. Ruddlesden–Popper hybrid lead iodide perovskite 2D homologous semiconductors. Chem. Mater. 28, 2852–2867 (2016).

    CAS  Google Scholar 

  16. 16.

    Tsai, H. et al. High-efficiency two-dimensional Ruddlesden–Popper perovskite solar cells. Nature 536, 312–316 (2016).

    CAS  PubMed  Google Scholar 

  17. 17.

    Wang, N. et al. Perovskite light-emitting diodes based on solution-processed self-organized multiple quantum wells. Nat. Photon. 10, 699–704 (2016).

    CAS  Google Scholar 

  18. 18.

    Yuan, M. et al. Perovskite energy funnels for efficient light-emitting diodes. Nat. Nanotechnol. 11, 872–877 (2016).

    CAS  PubMed  Google Scholar 

  19. 19.

    Mao, L. L. et al. Tunable white-light emission in single-cation-templated three-layered 2D perovskites (CH3CH2NH3)4Pb3Br10–xClx. J. Am. Chem. Soc. 139, 11956–11963 (2017).

    CAS  PubMed  Google Scholar 

  20. 20.

    Proppe, A. H. et al. Synthetic control over quantum well width distribution and carrier migration in low-dimensional perovskite photovoltaics. J. Am. Chem. Soc. 140, 2890–2896 (2018).

    CAS  PubMed  Google Scholar 

  21. 21.

    Shi, E. et al. Two-dimensional halide perovskite nanomaterials and heterostructures. Chem. Soc. Rev. 47, 6046–6072 (2018).

  22. 22.

    Mitzi, D. B. Templating and structural engineering in organic–inorganic perovskites. J. Chem. Soc. Dalton Trans. 0, 1–12 (2001).

    CAS  Google Scholar 

  23. 23.

    Saparov, B. & Mitzi, D. B. Organic–inorganic perovskites: structural versatility for functional materials design. Chem. Rev. 116, 4558–4596 (2016).

    CAS  PubMed  Google Scholar 

  24. 24.

    Braun, M., Tuffentsammer, W., Wachtel, H. & Wolf, H. C. Pyrene as emitting chromophore in organic-inorganic lead halide-based layered perovskites with different halides. Chem. Phys. Lett. 307, 373–378 (1999).

    CAS  Google Scholar 

  25. 25.

    Chondroudis, K. & Mitzi, D. B. Electroluminescence from an organic-inorganic perovskite incorporating a quaterthiophene dye within lead halide perovskite layers. Chem. Mater. 11, 3028–3030 (1999).

    CAS  Google Scholar 

  26. 26.

    Mitzi, D. B., Chondroudis, K. & Kagan, C. R. Design, structure, and optical properties of organic-inorganic perovskites containing an oligothiophene chromophore. Inorg. Chem. 38, 6246–6256 (1999).

    CAS  PubMed  Google Scholar 

  27. 27.

    Takeoka, Y., Asai, K., Rikukawa, M. & Sanui, K. Incorporation of conjugated polydiacetylene systems into organic–inorganic quantum-well structures. Chem. Commun. 2592–2593 (2001).

  28. 28.

    Zhu, X. H. et al. Effect of mono- versus di-ammonium cation of 2,2′-bithiophene derivatives on the structure of organic–inorganic hybrid materials based on iodo metallates. Inorg. Chem. 42, 5330–5339 (2003).

    CAS  PubMed  Google Scholar 

  29. 29.

    Ema, K., Inomata, M., Kato, Y., Kunugita, H. & Era, M. Nearly perfect triplet-triplet energy transfer from wannier excitons to naphthalene in organic–inorganic hybrid quantum-well materials. Phys. Rev. Lett. 100, 257401 (2008).

    CAS  PubMed  Google Scholar 

  30. 30.

    Era, M., Kobayashi, T., Sakaguchi, K., Tsukamoto, E. & Oishi, Y. Electric conduction of PbBr-based layered perovskite organic–inorganic superlattice having carbazole chromophore-linked ammonium molecule as an organic layer. Org. Electron. 14, 1313–1317 (2013).

    CAS  Google Scholar 

  31. 31.

    Papavassiliou, G. C., Mousdis, G. A., Pagona, G., Karousis, N. & Vidali, M.-S. Room temperature enhanced blue-green, yellow-orange and red phosphorescence from some compounds of the type (CH3NH3)n−1(1-naphthylmethyl ammonium)2Pbn(ClxBr1–x)3n+1 (with n = 1, 2 and 0 ≤ x ≤1) and related observations from similar compounds. J. Lumin. 149, 287–291 (2014).

    CAS  Google Scholar 

  32. 32.

    Evans, H. A. et al. (TTF)Pb2I5: a radical cation-stabilized hybrid lead iodide with synergistic optoelectronic signatures. Chem. Mater. 28, 3607–3611 (2016).

    CAS  Google Scholar 

  33. 33.

    Cortecchia, D., Soci, C., Cametti, M., Petrozza, A. & Marti-Rujas, J. Crystal engineering of a two-dimensional lead-free perovskite with functional organic cations by second-sphere coordination. Chempluschem 82, 681–685 (2017).

    CAS  PubMed  Google Scholar 

  34. 34.

    Du, K. Z. et al. Two-dimensional lead(ii) halide-based hybrid perovskites templated by acene alkylamines: crystal structures, optical properties, and piezoelectricity. Inorg. Chem. 56, 9291–9302 (2017).

    CAS  PubMed  Google Scholar 

  35. 35.

    Ortiz-Cervantes, C., Román-Román, P. I., Vazquez-Chavez, J., Hernández-Rodríguez, M. & Solis-Ibarra, D. Thousand-fold conductivity increase in 2D perovskites by polydiacetylene incorporation and doping. Angew. Chem. Int. Ed. 57, 13882–13886 (2018).

    CAS  Google Scholar 

  36. 36.

    Passarelli, J. V. et al. Enhanced out-of-plane conductivity and photovoltaic performance in n = 1 layered perovskites through organic cation design. J. Am. Chem. Soc. 140, 7313–7323 (2018).

    CAS  PubMed  Google Scholar 

  37. 37.

    Mitzi, D. B. Synthesis, crystal structure, and optical and thermal properties of (C4H9NH3)2MI4 (M = Ge, Sn, Pb). Chem. Mater. 8, 791–800 (1996).

  38. 38.

    Billing, D. G. & Lemmerer, A. Synthesis, characterization and phase transitions in the inorganic-organic layered perovskite-type hybrids [(CnH2n+1NH3)2PbI4], n = 4, 5 and 6. Acta Crystallogr. B 63, 735–747 (2007).

    CAS  PubMed  Google Scholar 

  39. 39.

    Liao, W.-Q. et al. A lead-halide perovskite molecular ferroelectric semiconductor. Nat. Commun. 6, 7338 (2015).

    PubMed  PubMed Central  Google Scholar 

  40. 40.

    Niu, W., Eiden, A., Vijaya Prakash, G. & Baumberg, J. J. Exfoliation of self-assembled 2D organic–inorganic perovskite semiconductors. Appl. Phys. Lett. 104, 171111 (2014).

    Google Scholar 

  41. 41.

    Straus, D. B. & Kagan, C. R. Electrons, excitons, and phonons in two-dimensional hybrid perovskites: connecting structural, optical, and electronic properties. J. Phys. Chem. Lett. 9, 1434–1447 (2018).

    CAS  PubMed  Google Scholar 

  42. 42.

    Zhu, T. et al. Highly mobile charge-transfer excitons in two-dimensional WS2/tetracene heterostructures. Sci. Adv. 4, eaao3104 (2018).

    PubMed  PubMed Central  Google Scholar 

  43. 43.

    Blum, V. et al. Ab initio molecular simulations with numeric atom-centered orbitals. Comput. Phys. Commun. 180, 2175–2196 (2009).

    CAS  Google Scholar 

  44. 44.

    Levchenko, S.V. et al. Hybrid functionals for large periodic systems in an all-electron, numeric atom-centered basis framework. Comput. Phys. Commun. 192, 60–69 (2015).

    CAS  Google Scholar 

  45. 45.

    Huhn, W.P. & Blum, V. One-hundred-three compound band-structure benchmark of post-self-consistent spin-orbit coupling treatments in density functional theory. Phys. Rev. Mater. 1, 033803 (2017).

    Google Scholar 

  46. 46.

    Liu, C. et al. Tunable semiconductors: control over carrier states and excitations in layered hybrid organic-inorganic perovskites. Phys. Rev. Lett. 121, 146401 (2018).

    CAS  PubMed  Google Scholar 

  47. 47.

    Leveillee, J. et al. Influence of π-conjugated cations and halogen substitution on the optoelectronic and excitonic properties of layered hybrid perovskites. Phys. Rev. Mater. 2, 105406 (2018).

    CAS  Google Scholar 

Download references

Acknowledgements

This work is supported by the US Office of Naval Research (award no. N00014-19-1-2296 to L.D.; programme managers: P. Armistead and J. Parker), the Davidson School of Chemical Engineering, College of Engineering and the Birck Nanotechnology Center of Purdue University. L.H., J.S and S.D acknowledge the support from US Department of Energy, Office of Basic Energy Sciences through award no. DE-SC0016356. B.W.B. acknowledges the support from US Air Force Office of Scientific Research (award no. FA9550-15-1-0449). The work on the single-crystal X-ray diffractions was supported by the National Science Foundation (award no. CHE 1625543). Work by V.B. and R.S. was financially supported by the National Science Foundation under award no. DMR-1729297. An award of computer time was provided by the Innovative and Novel Computational Impact on Theory and Experiment Program. This research used resources of the Argonne Leadership Computing Facility, which is a Department of Energy Office of Science User Facility supported under contract no. DE-AC02-06CH11357. S.J. thanks the Deutsche Forschungsgemeinschaft (German Research Foundation) for a postdoctoral fellowship (award no. 393196393). Transmission electron microscopy work is supported by the Center for High-resolution Electron Microscopy at ShanghaiTech University. The authors thank G. Wiederrecht and R. Schaller for assistance in the streak camera measurements; D. Zemlyanov for the ultraviolet photoelectron spectroscopy measurements; D. Kumar for grazing-incidence wide-angle X-ray scattering data processing; J. Mei for cyclic voltammetry measurements; and S. Beaudoin for atomic force microscopy measurements.

Author information

Affiliations

Authors

Contributions

L.D. conceived the idea and supervised the project. Y.G. carried out the materials synthesis, structural characterizations and data analysis. E.S. synthesized the nanocrystals. J.S., S.D. and L.H. carried out the ultrafast spectroscopy measurements and data analysis. S.B.S. and B.S. performed molecular dynamics simulations. C.L., B.Y. and Y.Y. carried out high-resolution transmission electron microscopy measurements and data analysis. A.L.-P. and C.Z. carried out grazing-incidence wide-angle X-ray scattering measurements. P.Y., P.L., R.S., S.J. and V.B. performed density functional theory simulations. M.Z. collected single-crystal X-ray data and solved and refined the crystal structures. B.W.B. provided characterization facilities and participated data analysis and manuscript preparation. Y.G. and L.D. wrote the manuscript. All authors discussed the results and revised the manuscript.

Corresponding author

Correspondence to Letian Dou.

Ethics declarations

Competing interests

The authors declare no competing interests.

Additional information

Publisher’s note Springer Nature remains neutral with regard to jurisdictional claims in published maps and institutional affiliations.

Supplementary information

Supplementary Information

Supplementary Figs., tables, methods and 1H, 13C NMR and FT-IR spectra.

Crystallographic data

CIF for compound (2T)2PbI4; CCDC reference: 1861843.

Crystallographic data

CIF for compound (4Tm)2PbI4; CCDC reference: 1846391.

Crystallographic data

CIF for compound (BTm)2PbI4; CCDC reference: 1846392.

Video

Water immersion test.

Rights and permissions

Reprints and Permissions

About this article

Verify currency and authenticity via CrossMark

Cite this article

Gao, Y., Shi, E., Deng, S. et al. Molecular engineering of organic–inorganic hybrid perovskites quantum wells. Nat. Chem. 11, 1151–1157 (2019). https://doi.org/10.1038/s41557-019-0354-2

Download citation

Further reading

Search

Quick links

Sign up for the Nature Briefing newsletter for a daily update on COVID-19 science.
Get the most important science stories of the day, free in your inbox. Sign up for Nature Briefing