Research ArticleMATERIALS SCIENCE

A chiral switchable photovoltaic ferroelectric 1D perovskite

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Science Advances  28 Feb 2020:
Vol. 6, no. 9, eaay4213
DOI: 10.1126/sciadv.aay4213
  • Fig. 1 Design principle.

    Lead halogen octahedra control the semiconducting property independently from the organic molecule that can be engineered to introduce a previously unknown properties, such as the simultaneous ferroelectricity and chirality achieved here.

  • Fig. 2 Structure determination.

    (A and B) Optical images of our materials prepared with a pair of enantiomers, R-CYHEAI and S-CYHEAL, with (C) needle-like crystals. (Photo credit (A, B, and C): Yang Hu, Rensselaer Polytechnic Institute). (D) NMR results of our material (synthesized with R-CYHEA) dissolved in DMSO-d6. (E) FTIR result of our material (synthesized with S-CYHEA). N─H bond peaks shows up at around 3200 cm−1, which is a little bit away from that of S-CYHEA but is almost the same as that of S-CYHEAI, indicating that this shift comes from the formation of ─NH3+. (F) Transmission spectrum with polarized light. The rotation of polarization direction indicates the existence of a single fast axis and the good single-crystal quality. (G) Single-crystal XRD diffraction pattern of our needle-like single crystal at −173°C. (H) Corresponding digitally reconstructed precession photograph of our crystal at 25°C, showing the (h0l) planes. (I) Schematic drawing of the structure of our 1D perovskite, where lead, iodine, carbon, nitrogen, and hydrogen atoms are represented by black, purple, brown, blue, and white spheres, respectively.

  • Fig. 3 Switchable photovoltaic ferroelectric effect.

    (A) TD-SHG reveals a transition from an inversion symmetry broken to an inversion-symmetric phase at 85°C. Inset: SHG peak at 540 nm from a 1080-nm infrared laser. a.u., arbitrary units. (B) PE loop of our perovskite confirming its ferroelectricity. Test was done at 800 Hz. (C) Switchable diode effect: After poling with +10 V and −10 V for 200 s, the photocurrent without bias is negative and positive, respectively, because of (D) band structure of our polycrystal device under zero bias, positive bias, and negative bias, respectively. A reversal in the band bending and resulting diode orientations are shown in the device. LED, light-emitting diode. PVK, perovskite. (E) Electronic band structure for chiral CYHEA (i and iii) and nonchiral CYHEA (ii and iv) XPbI3 (i and ii) and X2PbI4 (iii and iv) stoichiometries including spin-orbit coupling (SOC). Bandgaps increase and switch from direct to indirect on going from X2PbI4 to XPbI3 for each material. Including SOC brings the gap in much closer agreement with the experimental absorbance results as shown in fig. S20.

  • Fig. 4 Single-crystal phase transition and pyroelectric study.

    (A) Temperature-dependent synchrotron XRD results. Intensity of peak (201) markedly decreases, which indicates a phase transition at around 100°C. More detailed results can be found in the Supplementary Materials and movies S1 and S2. (B) DSC results. Sudden increase and decrease indicate a phase transition at around 100°C. (C) Temperature dependence of real part of dielectric constant. A peak at around 100°C indicates a phase transition. (D) Temperature dependence of pyroelectric current. The red and blue curves are fitting to Landau theory and polarization versus temperature curve obtained by integration, respectively. The peak at around 100°C indicates a phase transition. Our experiment results fit well with Landau theory, and the polarization at room temperature is around 1.2 μC/cm2 based on integration. (E) Pyroelectric coefficient versus poling electric field loop. Dash line is a trend line showing a hysteresis.

  • Fig. 5 Chirality.

    (A) Schematic of CD measurements: Chiral material absorbs different amount of LCP and RCP lights, changing linear polarization to elliptical. LP, linearly polarized. (B) CD spectrum of the synthesized crystals show opposite signals at the same position, indicating that they are enantiomers. (C) Our chiral ferroelectric material surpasses the CD signals of conventional chiral materials. RNase, ribonuclease; HEWL, hen egg white lysozyme.

Supplementary Materials

  • Supplementary material for this article is available at http://advances.sciencemag.org/cgi/content/full/6/9/eaay4213/DC1

    Section S1. Structural characterization

    Section S2. Optical characterization

    Section S3. Ferroelectricity and pyroelectricity

    Section S4. Photoferroelectricity

    Section S5. Chirality

    Fig. S1. NMR result of R-CYHEA.

    Fig. S2. FTIR result of R-CYHEAI.

    Fig. S3. Raman results of R-CYHEAPbI3 on KCl.

    Fig. S4. Powder XRD result of R-CYHEAPbI3.

    Fig. S5. Powder XRD result of S-CYHEAPbI3.

    Fig. S6. XRD result of R-CYHEAPbI3 grown on Si.

    Fig. S7. XRD result of R-CYHEAPbI3 grown on mica.

    Fig. S8. XRD result of R-CYHEAPbI3 grown on NaCl.

    Fig. S9. Rietveld modeling (red curve) of room temperature powder x-ray data (black crosses) and corresponding difference curve (blue) for powdered R-CYEHAPbI3.

    Fig. S10. Single-crystal XRD results of R-CYEHAPbI3.

    Fig. S11. Diffraction analysis.

    Fig. S12. Single-crystal synchrotron XRD results.

    Fig. S13. Analysis of synchtrotron diffraction result.

    Fig. S14. Peak intensities have changed after temperature increases from 0° to 175°C.

    Fig. S15. EBSD of single-crystal sample.

    Fig. S16. Schematic drawing of the system that we used to measure the volume of the crystal in density determination.

    Fig. S17. Theoretical electronic band structure and polarization.

    Fig. S18. PL of R-CYEHAPbI3.

    Fig. S19. Transmission spectrum of S-CYEHAPbI3.

    Fig. S20. Absorption spectrum of S-CYEHAPbI3.

    Fig. S21. Photoresponse of R-CYEHAPbI3 on FTO under 405-nm laser.

    Fig. S22. Photoresponse of R-CYEHAPbI3 on FTO under 635-nm laser.

    Fig. S23. SHG spectrum of R-CYEHAPbI3.

    Fig. S24. Comparison of Sawyer-Tower method and double wave method used in PE loop measurements.

    Fig. S25. Our single-crystal device.

    Fig. S26. Orientation dependent of I-V curves of R-CYEHAPbI3.

    Fig. S27. Pyroelectric results.

    Fig. S28. Polarization retention and fatigue endurance.

    Fig. S29. Photoferroelectric measurements.

    Fig. S30. Voltage-dependent photoresponse.

    Fig. S31. Comparison of the CD signals of chiral perovskites and chiral precursors.

    Fig. S32. Schematic drawing of the generation of ellipticity from different absorption to LCP and RCP.

    Table S1. Crystallographic and refinement parameters for R-CYEHAPbI3.

    Table S2. Fractional coordinates and isotropic displacement parameters.

    Table S3. Bond lengths and angles.

    Movie S1. Laue diffraction patterns versus temperature.

    Movie S2. Zoom-in of Laue diffraction patterns versus temperature.

  • Supplementary Materials

    The PDF file includes:

    • Section S1. Structural characterization
    • Section S2. Optical characterization
    • Section S3. Ferroelectricity and pyroelectricity
    • Section S4. Photoferroelectricity
    • Section S5. Chirality
    • Fig. S1. NMR result of R-CYHEA.
    • Fig. S2. FTIR result of R-CYHEAI.
    • Fig. S3. Raman results of R-CYHEAPbI3 on KCl.
    • Fig. S4. Powder XRD result of R-CYHEAPbI3.
    • Fig. S5. Powder XRD result of S-CYHEAPbI3.
    • Fig. S6. XRD result of R-CYHEAPbI3 grown on Si.
    • Fig. S7. XRD result of R-CYHEAPbI3 grown on mica.
    • Fig. S8. XRD result of R-CYHEAPbI3 grown on NaCl.
    • Fig. S9. Rietveld modeling (red curve) of room temperature powder x-ray data (black crosses) and corresponding difference curve (blue) for powdered R-CYEHAPbI3.
    • Fig. S10. Single-crystal XRD results of R-CYEHAPbI3.
    • Fig. S11. Diffraction analysis.
    • Fig. S12. Single-crystal synchrotron XRD results.
    • Fig. S13. Analysis of synchtrotron diffraction result.
    • Fig. S14. Peak intensities have changed after temperature increases from 0° to 175°C.
    • Fig. S15. EBSD of single-crystal sample.
    • Fig. S16. Schematic drawing of the system that we used to measure the volume of the crystal in density determination.
    • Fig. S17. Theoretical electronic band structure and polarization.
    • Fig. S18. PL of R-CYEHAPbI3.
    • Fig. S19. Transmission spectrum of S-CYEHAPbI3.
    • Fig. S20. Absorption spectrum of S-CYEHAPbI3.
    • Fig. S21. Photoresponse of R-CYEHAPbI3 on FTO under 405-nm laser.
    • Fig. S22. Photoresponse of R-CYEHAPbI3 on FTO under 635-nm laser.
    • Fig. S23. SHG spectrum of R-CYEHAPbI3.
    • Fig. S24. Comparison of Sawyer-Tower method and double wave method used in PE loop measurements.
    • Fig. S25. Our single-crystal device.
    • Fig. S26. Orientation dependent of I-V curves of R-CYEHAPbI3.
    • Fig. S27. Pyroelectric results.
    • Fig. S28. Polarization retention and fatigue endurance.
    • Fig. S29. Photoferroelectric measurements.
    • Fig. S30. Voltage-dependent photoresponse.
    • Fig. S31. Comparison of the CD signals of chiral perovskites and chiral precursors.
    • Fig. S32. Schematic drawing of the generation of ellipticity from different absorption to LCP and RCP.
    • Table S1. Crystallographic and refinement parameters for R-CYEHAPbI3.
    • Table S2. Fractional coordinates and isotropic displacement parameters.
    • Table S3. Bond lengths and angles.

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    Other Supplementary Material for this manuscript includes the following:

    • Movie S1 (.avi format). Laue diffraction patterns versus temperature.
    • Movie S2 (.avi format). Zoom-in of Laue diffraction patterns versus temperature.

    Files in this Data Supplement:

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