advances.sciencemag.org/cgi/content/full/3/8/e1716/dc1 Supplementary Materials for Polymer-modified halide perovskite films for efficient and stable planar heterojunction solar cells Lijian Zuo, Hexia Guo, Dane W. dequilettes, Sarthak Jariwala, Nicholas De Marco, Shiqi Dong, Ryan DeBlock, David S. Ginger, Bruce Dunn, Mingkui Wang, Yang Yang This PDF file includes: Published 23 August 217, Sci. Adv. 3, e1716 (217) DOI: 1.1126/sciadv.1716 fig. S1. Interactions between the perovskite precursors (PbI2 and MAI) and polymers. fig. S2. FTIR spectra of perovskite (PVSK), polyethylenimine (PEI), and perovskite/polyethylenimine (PVSK + PEI) films. fig. S3. GDOES (O element) of perovskite films processed and measured under the same condition. fig. S4. Surface morphology of perovskite films. fig. S. XRD patterns of perovskite film with and without different polymers. fig. S6. I-V characteristic curves of perovskite solar cells with PVP grain boundary passivation. fig. S7. EQE spectra of perovskite solar cells versus photon energy. fig. S8. I-V characteristic of perovskite solar cells with different amount of PVP. fig. S9. I-V characteristic of perovskite solar cells (made from compact PbI2) with and without PVP. fig. S1. Histogram of device efficiency distribution of perovskite solar cells with different polymers. fig. S11. I-V hysteresis behavior of perovskite solar cells with and without different polymer passivation. fig. S12. Depth-dependent PL behavior of perovskite film with or without PVP. fig. S13. A typical Nyquist plot for a PVP device at an open-circuit voltage under 1-sun illumination in the frequency range of 2 Hz to 1 MHz. fig. S14. Binding energy dependent device performance. fig. S1. Interactions between MAI and the polymers.
a) b) 1 2 3 4 fig. S1. Interactions between the perovskite precursors (PbI2 and MAI) and polymers. Authentic picture of a) the PbI2:MAI DMF solution with different polymers: 1. Bare PbI2:MAI DMF solution, 2. PbI2:MAI DMF solution with PVP polymers, 3. PbI2:MAI DMF solution with b-pei polymers, 4. PbI2:MAI DMF solution with PAA polymers. b) PbI2:MAI:poly (4-vinylpyridine) (PVP) solution. It is clear that a gel forms in this system due to the strong interaction between the PVP and Pb 2+. Absorbance (a.u.) PVSK PEI-PVSK PEI 1 1 2 2 3 3 4 Wave number (cm -1 ) fig. S2. FTIR spectra of perovskite (PVSK), polyethylenimine (PEI), and perovskite/polyethylenimine (PVSK + PEI) films.
Intensity (a.u.) 6 4 3 2 O Perovskite-1 Perovsktie-2 1 2 4 6 8 1 Sputter time (s) fig. S3. GDOES (O element) of perovskite films processed and measured under the same condition. a) b) 1 μm 1 μm c) d) 1 μm 1 μm fig. S4. Surface morphology of perovskite films. a) without any polymer, b) with PVP, c) with PAA, d) with PEI modification.
Intensity (a.u.) 8 6 4 2 72 48 24 7 2 Perovskite:PEI Perovskite:PVP Perovskite:PAA 8 Perovskite 6 4 2 1 1 2 2 3 3 4 4 2 (degree) fig. S. XRD patterns of perovskite film with and without different polymers. J (ma/cm 2 ) - -1-1 Perovskite solar cells with PVP grain boundary passivation V OC =1.16 PCE 19.78% J SC = 21.71 ma/cm 2 FF=.79-2 -.2..2.4.6.8 1. 1.2 fig. S6. I-V characteristic curves of perovskite solar cells with PVP grain boundary passivation. The VOC reaches a maximum value of 1.16 V.
1 EQE (%) 1 1 Ref 1 PVP PAA PEI 1 1. 2. 2. 3. 3. 4. 1. 1. 1.6 1.6 1.7 1.7 1.8 1.8 Photon energy (ev) fig. S7. EQE spectra of perovskite solar cells versus photon energy. A absorbing edge of ~ 1. ev can be deduced. 4 J (ma/cm 2 ) -4-8 -12-16 -2 2:1 1:1 :1 1:1-24 -.2..2.4.6.8 1. 1.2 fig. S8. I-V characteristic of perovskite solar cells with different amount of PVP.
J (ma/cm 2 ) 1 - -1-1 -2 Ref PVP -.2..2.4.6.8 1. 1.2 fig. S9. I-V characteristic of perovskite solar cells (made from compact PbI2) with and without PVP. The PVP is spin-coated on to the perovskite film. The PVP is dissolved in IPA with a concentration of.1 mg/ml. a) b) Number of device pixel(/) 1 1 Ref Gauss fitting 14 1 16 17 18 19 2 21 PCE (%) Number of device pixel (/) c) 2 d) PAA Gauss fitting Number of device pixel (/) 1 1 Number of device pixel (/) 3 3 2 2 1 1 PVP Gauss fitting 14 1 16 17 18 19 2 21 16 12 8 4 PCE (%) PEI Gauss fitting 14 1 16 17 18 19 2 21 PCE (%) 14 1 16 17 18 19 2 21 PCE (%) fig. S1. Histogram of device efficiency distribution of perovskite solar cells with different polymers. a) without any polymers, b) with PVP, c) with PAA, d) with PEI.
a) b) J (ma/cm 2 ) - -1-1 Reverse scan Forward scan J (ma/cm 2 ) - -1-1 Reverse scan Forward scan -2-2 -.2..2.4.6.8 1. 1.2 c) d) -.2..2.4.6.8 1. 1.2 J (ma/cm 2 ) - -1-1 Reverse scan Forward scan J (ma/cm 2 ) - -1-1 Reverse scan Forward scan -2-2 -.2..2.4.6.8 1. 1.2 -.2..2.4.6.8 1. 1.2 fig. S11. I-V hysteresis behavior of perovskite solar cells with and without different polymer passivation. a) without any polymer, b) PVP polymer, c) PAA polymer, d) PEI polymer.
a) Front side or perovskite top side b) perovskite glass perovskite glass back side or glass side c) d) PL intensity (a.u.) 6.k 4.k 2.k Front side Back side PL intensity (a.u.) 8.k 6.k 4.k 2.k Front side Back side.. 68 7 72 74 76 78 8 82 84 86 Wavelength (nm) 68 7 72 74 76 78 8 82 84 86 Wavelength (nm) e) 6k k Front side Back side f) 7k 6k Front side Back side PL intensity (a.u.) 4k 3k 2k 1k PL intensity (a.u.) k 4k 3k 2k 1k g) 68 7 72 74 76 78 8 82 84 86 Wavelength (nm) 68 7 72 74 76 78 8 82 84 86 Wavelength (nm) 1. Absorbed light (1%).8.6.4.2. Absorbed light @ 64 nm 1 2 3 4 6 7 Thickness of perovskite (nm) fig. S12. Depth-dependent PL behavior of perovskite film with or without PVP. a) schematic diagram for top or front side excitation, b) schematic diagram for glass side or back side excitation. PL spectroscopy of perovskite films: c) perovskite film processed from compact PbI2 without polymer, d) perovskite film processed from mesoporous PbI2 without PVP, e) perovskite film processed from compact PbI2 with PVP, f) perovskite film processed from mesoporous PbI2 with PVP. Black curve: from front
side, red curve: from glass side. g) absorbing profile of 64 nm light on different position of perovskite film (structure: perovskite/glass, illuminated from the perovskite side). -Z'' / R s C R PVP fitting 1 1 Z' / fig. S13. A typical Nyquist plot for a PVP device at an open-circuit voltage under 1-sun illumination in the frequency range of 2 Hz to 1 MHz. The resulting frequency analysis shows two peaks. In the order of increasing frequency these elements are attributed to the ion motion in MAPbI3-xClx, the electron transfer at the MAPbI3-xClx/SnO2 or MAPbI3-xClx/spiro-OMeTAD (i.e. interfacial charge recombination). Our interests are focused on the first semi-arc, which can be fitted with the equivalent circuit model as shown in the inset. The R is the charge transfer resistance of the charge recombination process at interferes and C is the correlated capacitance.
2 PCE Range (%) 1 1 PEI PVP PAA Ref Ammonium Pyridine Carboxylic Ref -- 37.7 1.71 Coordination energy (kj/mol) -- fig. S14. Binding energy dependent device performance.
MAI b- PEI MAI:b- PEI MAI PVP MAI:PVP
fig. S1. Interactions between MAI and the polymers. a) Pictures of solutions with isopropanol as solvents: pristine MAI (7 mg/ml) 1 &2, pristine PVP (2 mg/ml) 3 & 8, pristine b-pei (2 mg/ml) 4 & 7, mixed solution of MAI:b-PEI (1:1 vol%), mixed solution of MAI:PVP 6, b-pei dropped with HI solution 9. b) H-NMR spectroscopies of MAI, b-pei, and MAI:b-PEI mixture. c) H-NMR spectroscopies of MAI, b-pvp, and MAI:PVP. As shown, the broad peak at 7.4 ppm is characteristic of hydrogen bonded to a nitrogen, and peak at 2.3 ppm is attributed to the hydrogen bonded to a carbon in MAI. After blending with b-pei, the characteristic peaks disappeared, which indicate the chemical reactions occurs between b-pei and MAI. The disappearance of the two peak is due to chemical reaction between MAI and b-pei induced precipitate from the solution (a to ). In case of PVP, two peaks at 6.6 and 8.3 can be attributed to the hydrogen on pyridine. After, blending with MAI solution, the two peaks remains. Most importantly, the characteristic peak at 2.3 ppm remains, as confirmed by the similar integrated area compared to the pristine MAI solution. These results suggested that the interaction between PVP and MAI is negligible, while strong chemical interaction occurs within MAI and b-pei.