© 2020 Wiley-VCH GmbH

Supporting Information
for Small, DOI: 10.1002/smll.202005216

Dual Defect-Passivation Using Phthalocyanine for Enhanced

Efficiency and Stability of Perovskite Solar Cells
Qikun Hu, Ehsan Rezaee, Wangping Xu, Rajendran
Ramachandran, Qian Chen, Hu Xu, Tarek EL-Assaad,
Dominic V. McGrath,* and Zong-Xiang Xu*
© 2020 Wiley-VCH GmbH

Supporting Information
Dual defect-passivation using phthalocyanine for enhanced efficiency and stability of
perovskite solar cells Title

Qikun Hu,# Ehsan Rezaee,# Wangping Xu,# Rajendran Ramachandran, Qian Chen, Hu Xu,
Tarek EL-Assaad, Dominic V. McGrath,* Zong-Xiang Xu*

Experimental
Materials
Unless specified otherwise, all materials were used as received. Organic solvents and

Ti(iOPr)4 and ZnCl2 were purchased from Sigma-Aldrich. CH3NH3I and PbI2 were purchased

from Xi’an Polymer Light Technology Corp. (Xian, China). Hexane-1-thiol,

2,3-dicyanohydroquinone, p-toluenesulfonyl chloride and potassium carbonate were

purchased from Sigma-Aldrich. 1,8-Diazabicyclo-[5,4,0]-undec-7-ene (DBU) was obtained

from TCI (Shang Hai, China).

Synthesis of Phthalocyanine
The synthesis of NP-SC6 -TiOPc and NP-SC6 -ZnPc was carried out according to the reported

procedure.[1] The 3,6-bis(hexylthio)phthalonitrile was prepared according to Scheme S1.

NP-SC 6 -TiOPc and NP-SC6 -ZnPc was prepared under templated cyclization conditions in the

presence of DBU (Scheme S1).

Synthesis of 3,6-bis(4’-methylphenylsulfonyloxy)phthalonitrile
As mixture of p-toluenesulfonyl chloride (5.1 g, 27 mmol), 2,3-dicyanohydroquinone (2.1 g,

13 mmol), potassium carbonate (6.9 g, 50 mmol) and acetone (15 mL) was heated to reflux

for 3 h. The reaction mixture was poured into 70 mL DI H2O and stirred for 30 min. A light

brown solid was isolated by filtration and washed with H2 O (4 × 30 mL). A soluble gray

impurity was removed by washing with acetone (2.0 mL) to afford

3,6-bis(4’-methylphenylsulfonyloxy)phthalonitrile as a colorless solid (5.3 g, 87%): 1H NMR

(500 MHz, CDCl3 ) δ 7.85-7.82 (m, 4H), 7.81 (s, 2H), 7.43-7.40 (m, 4H), 2.50(s, 6H).
Synthesis of 3,6-bis(hexylthio)phthalonitrile
A mixture of hexane-1-thiol (3.5g, 30 mmol), K2CO 3 (5.5 g, 40 mmol) and DMSO (100 mL)

was stirred at RT for 30 min. To the mixture,

3,6-bis(4’-methylphenylsulfonyloxy)phthalonitrile (4.7 g, 10 mmol) was slowly added and

the reaction mixture was maintained at RT for 12 h. The crude reaction mixture was diluted

with H2O (200 mL) and extracted into chloroform (2 × 100 mL) and dichloromethane (2 ×

150 mL). The combined organic extracts were further washed with 5% Na2CO3 (2 × 100 mL)

and H2O (2 × 100 mL). After removal of solvent under reduced pressure, a yellow solid was

collected. Purification of the yellow solid was conducted by recrystallization from EtOH (20

mL) twice to give 3,6-bis(hexylthio)phthalonitrile as a bright yellow solid (2.9 g, 81%): 1H

NMR (500 MHz, CDCl3) δ 7.49 (s, 2H), 3.03-3.00 (t, 4H), 1.71-1.65 (m, 4H), 1.48-1.42 (m,

4H), 1.31-1.29 (m, 8H), 0.91-0.88 (t, 6H).

Synthesis of 1,4,8,11,15,18,22,25-octakis(hexylthio)phthalocyaninato oxotitanium(II)

(NP-SC6 -TiOPc)
To a refluxing mixture of 3,6-bis(hexylthio)phthalonitrile (0.36 g, 1.0 mmol) and DBU (0.21

g, 1.4 mmol) in 1-pentanol (2.8 mL), Ti(iOPr)4 (0.077 g, 0.27 mmol) was added. The mixture

was maintained at reflux (150 °C) for 12 h. The mixture was allowed to cool to room

temperature and concentrated under reduced pressure. The residue was dissolved in CHCl3 (3

mL) and subjected to flash chromatography (SiO2, 3:97 MeOH/CHCl3) to achieve

1,4,8,11,15,18,22,25 octakis(hexylthio)phthalocyaninato oxotitanium (IV) as a purple solid

(64 mg, 17%): UV-Vis (λmax, nm) 850 nm; Elemental analysis calcd. (%) for

C80H112N8OS8Ti: C, 63.80; H, 7.50; N, 7.44. Found: C, 64.01; H, 7.48; N, 7.60.

Synthesis of 1,4,8,11,15,18,22,25-octakis(hexylthio)phthalocyaninato Zinc(II)

(NP-SC6-ZnPc)
To a refluxing mixture of 3,6-bis(hexylthio)phthalonitrile (0.36 g, 1.0 mmol) and DBU (0.21

g, 1.4 mmol) in 1-pentanol (2.8 mL), ZnCl2 (0.033 g, 0.27 mmol) was added. The mixture

was maintained at reflux (150 °C) for 12 h. The mixture was allowed to cool to room
temperature and concentrated under reduced pressure. The residue was dissolved in CHCl3 (3

mL) and subjected to flash chromatography (SiO2, 3:97 MeOH/CHCl3) to achieve

1,4,8,11,15,18,22,25 octakis(hexylthio)phthalocyaninato Zinc (II) as a blue solid (62 mg, 16

％): UV-Vis (λ max, nm) 833 nm; Elemental analysis calcd. (%) for C80H112 N8S8Zn: C, 63.79;

H, 7.50; N, 7.44. Found: C, 64.22; H, 7.58; N, 7.32.

Structure Characterization
X-ray diffraction patterns of the films deposited on FTO substrates were recorded using a

Smartlab 9 kW diffractometer with a Göbel mirror attachment. Irradiation of the parallel

CuKα1, 2 X-ray beams were fixed at a grazing incident angle (θ) of 2.000°. The detector was

independently moved to collect diffraction data in the 2θ range (3–30°) with a step size of

0.02° (2θ) at a fixed speed of 1 s/step. The morphologies of the thin-film samples were

determined by atomic force microscopy (AFM) using a Keysight Technologies

(5500AFM/STM) scanning probe microscope in tapping mode. The steady-state

photoluminescence spectra were measured with a FLS980 Spectrometer (Edinburgh

Instruments). The excitation light wavelength was 475 nm and the samples were various

perovskites. Time-resolved photoluminescence decay curves were acquired for the perovskite

films on FTO glass and for the perovskite/FTO glass stack (excitation using a

405-nm-wavelength pulsed laser). The contact angle measurements of perovskites were

performed using a Drop Shape Analyzer (DSA 25S, KRUSS). The morphology and

elemental mapping of the prepared samples were analyzed with the Scanning Electron

Microscope (SEM, Zeiss Merlin). The chemical states of the elements in samples were

identified with the X-ray photoelectron spectroscopy (XPS, ESCALB 250Xi) with Mg K

radiation. The highest occupied molecular orbital energy (HOMO) level of NP-SC6 -ZnPc

was measured by an ionization energy measurement system with the ionization photoelectron
spectrometer model (IPS-4). The UV-vis spectrum of NP-SC6 -ZnPc film on FTO was

recorded with a PerkinElmer Lambda750S spectrophotometer.

Fabrication and measurement of PSCs

FTO glasses were washed with cleaning fluid, deionized water, ethanol, acetone, and

isopropanol, sequentially. SnO2 based electron transporting layer (ETL) preparation was

reported as before.[2] The as-deposited ETLs were then treated with UV-Ozone for 20 min.

Finally, the ETL substrates were transferred to the glove box (H 2O content <0.01 ppm). The

perovskite absorber layers (~ 500 nm) were deposited on the ETL by using a modified

solvent engineering method.[3] The MAPbI3 perovskite precursor solution was prepared by

dissolving MAI (1.0 M) and PbI2 (1.0 M) in mixed solvent consisting of 632 μL DMF and 71

μL DMSO. Dozen microliters of the precursor solution was spin-coated on FTO/SnO2

substrate at 4000 rpm for 20 s in glove box, then a 0.3 mL antisolvent of chlorobenzene or

chlorobenzene containing NP-SC6 -TiOPc/NP-SC6 -ZnPc (with optimized concentration of 0.5

mg/mL) was quickly dropped when ten seconds passed. Finally, the substrate was heated at

65 °C for two minutes, then 100 °C for ten minutes. The thickness of the photosensitive layer

was measured using an Ambios Technology (Santa Cruz, CA) XP-2 profilometer. The

precursor solution of Spiro-OMeTAD layer was prepared by dissolving 72.3 mg

spiro-MeOTAD, 28.8 μL 4-tert-butylpyridine, 17.5 μL lithium

bis(trifluoromethylsulphonyl)imide acetonitrile solution (520 mg mL-1) into 1 mL

chlorobenzene. Then, the doped spiro-MeOTAD layer was deposited on top of the perovskite

layer by spin coating at 3000 rpm for 30 s. Finally, a 100 nm Au electrode was thermally

evaporated under high vacuum (<10−4 Pa) on top of the device. The active area of the device

was 0.11 cm2 , defined by the aperture area of the mask. The as fabricated perovskite samples

or PSC devices were denoted as MAPbI3 , MAPbI3/TiOPc and MAPbI 3/ZnPc for using

antisolvents of chlorobenzene, NP-SC6 -TiOPc/chlorobenzene, and

NP-SC 6 -ZnPc/chlorobenzene solution, respectively. The photocurrent-voltage (J-V)

characteristics of the devices were measured with a Keithley 2400 digital source meter at a

scan speed of 100 mV s-1 . The simulated AM 1.5G sunlight with an irradiance equivalent to

100 mW cm-2 was generated by an Oriel Solar 3A solar simulator and the intensity was

calibrated with an VLSI standard incorporated PN 91150V Si reference cell. For the

long-term stability measurement, the as-fabricated PSC devices without encapsulation were

stored in atmosphere with relative humidity of ~75% and at room temperature exposing to

room light. After each 4 days, the photocurrent-voltage (J-V) characteristics of the devices

were measured under simulated AM 1.5G sunlight with an irradiance equivalent to 100 mW

cm-2 . Steady-state output of the photocurrent and PCE was measured with a Keithley 2400

digital source meter under a certain bias. Dark current was measured with a Keithley 2400

digital source meter without illumination. The external quantum efficiency (EQE) spectrum

was measured using a solar cell QE/EQE measurement system (Zolix Solar Cell Scan 100)

model SR830 DSP lock-in amplifier coupled with a WDG3 monochromator and a 500 W

xenon lamp. Electrochemical impedance spectroscopy (EIS) testing was conducted on a

CIMPS-4 system (Zahner, ZOYPE).

DFT Calculations
All calculations were implemented by the Vienna Ab Initio Simulation Package (VASP).[4]

The generalized gradient approximation parameterized by Perdew-Burke-Ernzerhof (PBE)

functional was adopted and the electron-ion interaction was performed by

projector-augmented wave.[5] The cut-off energy was set to be 500 eV and the k-points mesh

was set to be 2 × 2 × 1 to optimize structures. The convergence threshold for the force was

set to be 0.02 eV/ Å. The slab consisting of a three-layer MAPbI3 (001) was built and the

vacuum was set to be 15 Å. The Van der Waals corrections (D3) were introduced to describe

the effect of Van der Waals interactions in all calculations.[6]

Scheme S1. Preparation method of (a) 3,6-disubstituted phthalonitrile; (b) NP-SC6 -TiOPc
and (c) NP-SC6 -ZnPc
Figure S1. (a) HOMO energy level and (b) UV-vis spectrum of ZnPc, and (c) Schematic
energy diagram of the materials used in this work. [1, 7]
Figure S2. XRD patterns of control MAPbI3 and passivated MAPbI3/NP-SC6 -ZnPc and
MAPbI3/NP-SC6 -TiOPc films.

Figure S3. AFM images of MAPbI 3 (a) before and (b) after washing by CB;
MAPbI3/NP-SC6 -TiOPc (c) before and (d) after washing by CB; MAPbI3 /NP-SC6 -ZnPc films
(e) before and (f) after washing by CB.
Figure S4. The full XPS scan survey spectra of bare Pc (left) and perovskite samples (right).

Figure S5. Deconvoluted XPS spectra of N and S of bare Pc (left) and Pc-passivated
perovskite.
Figure S6. The steady-state current output and PCE of (a) the pristine MAPbI3 and (b)
MAPbI3/NP-SC6 -ZnPc based PSCs.

Figure S7. The statistics for the photovoltaic parameters, including PCE, VOC, JSC, and FF, of
20 devices fabricated from the same batch.
Figure S8. Water droplet angle measurement stability results for PSCs based on (a) pristine
MAPbI3, (b) MAPbI3/NP-SC6 -TiOPc, and (c) MAPbI 3/NP-SC6 -ZnPc films.

Figure S9. Water resistance measurement for PSCs based on pristine MAPbI3,
MAPbI3/NP-SC6-TiOPc, and MAPbI3 /NP-SC6 -ZnPc films.
Figure S10. Thermal stability results for PSCs based on (a) pristine MAPbI3 , (b)
MAPbI3/NP-SC6 -TiOPc, and (c) MAPbI 3/NP-SC6 -ZnPc films.

Table S1. Summary of the parameters from fitting to the TRPL measurement data.
Perovskite A1 τ1 (ns) A2 τ2 (ns) τavg (ns)*

MAPbI3 0.43409 5.22722 0.58349 94.92203 91.39199

MAPbI3/ZnPc 0.3299 10.06676 0.69365 90.59549 86.55336

MAPbI3/TiOPc 0.36668 18.60014 0.71429 124.67603 117.13008

𝐴𝑖 𝜏𝑖2
*𝜏𝑎𝑣𝑔 =
𝐴𝑖 𝜏𝑖

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