Copyright WILEY-VCH Verlag GmbH & Co. KGaA, 69469 Weinheim, Germany, 2013.

Supporting Information

for Adv. Mater., DOI: 10.1002/adma. 201304803

Perovskite-Based Hybrid Solar Cells Exceeding 10%

Efficiency with High Reproducibility Using a Thin Film
Sandwich Approach

Bert Conings,* Linny Baeten, Christopher De Dobbelaere,

Jan D’Haen, Jean Manca, and Hans-Gerd Boyen
 Submitted to
Copyright WILEY-VCH Verlag GmbH & Co. KGaA, 69469 Weinheim, Germany, 2013.

Supporting Information

for Adv. Mater., DOI: 10.1002/adma.201304803

Perovskite-based hybrid solar cells exceeding 10% efficiency with high reproducibility

using a thin film sandwich approach

Bert Conings*, Linny Baeten, Christopher De Dobbelaere, Jan D'Haen, Jean Manca, Hans-

Gerd Boyen

Experimental details

Synthesis of the perovskite precursor. The precursor was prepared following a slightly

adapted procedure from Lee et al.[1] Briefly, 10 ml of hydroiodic acid (57% in water, Sigma)

was added dropwise to 24 ml of methylamine (33% in absolute ethanol, Sigma) and 100 ml

ethanol under nitrogen atmosphere. A rotary evaporator was used to remove the solvent and

crystallize methylammonium iodide (MAI). The precipitate was washed with diethyl ether

three times. The resulting white powder was dried on a hotplate at 65°C for 6 h in air. MAI

and PbCl2 (Alfa, 99.999%) were dissolved in dimethyl sulfoxide (Sigma) in separate vials and

then mixed to obtain a precursor solution with a MAI:PbCl2 molar ratio of 3:1 and a total

material content between 22.5 wt% and 60 wt%.

Fabrication of thin-film perovskite solar cells. Patterned ITO substrates (15 Ohm/sq,

Jinfung Limited, China) were cleaned by subsequent sonication in soap solution, water,
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acetone, and finally in boiling isopropanol (10 min. for each step), after which they were

treated with O2 plasma (50W, 3 min. at 0.5 mbar). The TiO2 blocking layer was deposited by

a previously reported aqueous solution-gel method.[2] In short, a glycolic acid based TiO2

precursor was spincoated at 3000 rpm for 30 s, followed by consecutive heating of 2 min. at

180°C, 2 min. at 300°C and 1 hour at 500°C. The substrates were then transferred to a

nitrogen-filled glovebox (<1 ppm O2 and H2O). Different thicknesses of the perovskite film

are obtained by changing the precursor concentration and/or spin speed of the perovskite

precursor (1500 or 3000 rpm for 5 minutes). After spincoating, the samples were heated at

100°C for 50 minutes. P3HT solution (Rieke Metals, 1.5 wt% in chlorobenzene, with a

molecular weight of 66kD and 93% regioregularity) was spincoated on top of the perovskite

at 1500 rpm. Immediately after, the samples were transferred to a vacuum evaporation system

where 200 nm of silver was evaporated at a pressure of ~1·106 mbar, defining cell areas of

3 to 5 mm2. Samples for optical measurements were made in the same fashion as solar cells,

but on glass substrates and without the silver electrode.

Characterization. JV-characterization was performed in N2 at room temperature under

AM1.5 of 100 mW/cm2 illumination with a Newport Oriel Class A model 91195A solar

simulator, using a black mask to delineate the device area.[3] The efficiency of the solar cells

was calculated using the formula: η = Jsc FF Voc / Pin,

with Pin the incoming light power and

FF (fill factor) = Jmpp Vmpp / (Jsc Voc) where Jmpp and Vmpp represent the current and voltage

values at the maximum power point of the JV curve.

The perovskite morphology was investigated on a FEI Quanta 200FEG-SEM. XRD was

measured with a Siemens D-5000 diffractometer with Cu Kα1 radiation. Perovskite layer

thicknesses were determined with a Dektak XT profilometer. Chemical analysis was carried

out on a commercial electron spectrometer (PHI-5600LS) with an X-ray source providing

monochromatized Al-Kα photons (1486.6 eV). Valence band spectroscopy was performed by

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applying either He-I (21.2 eV) or Al-Kα radiation. The overal energy resolution (electrons +

photons) was set to 0.03 eV (FWHM) for UPS and 0.30 eV (FWHM) for XPS operation. In

all cases, the electron energy analyzer was operated in constant pass energy mode. In order to

perform a chemical analysis, appropriate core-levels (C-1s, N-1s, Pb-4f, I-3d and Cl-2p) were

measured and peak areas were integrated using a Shirley type of background.[4] By taking into

account appropriate photoexcitation cross-sections[5] the distribution of elements was derived

following standard procedures.[6] Optical absorption measurements were acquired on a

Varian Cary UV-vis spectrometer. Photoluminesence spectra were taken with a Horiba-Jobin

Yvon Fluorolog-3 device, with an excitation wavelength of 450 nm.

Figure S1: XPS spectrum of the hole collecting layer P3HT as used in the thin-film perovskite

solar cells, illustrating the purity of the material. Integration of the peak areas yields a C:S

ratio of exactly 10:1, the expected value from the molecular structure.

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[1] M. M. Lee, J. Teuscher, T. Miyasaka, T. N. Murakami, H. J. Snaith, Science 2012,

338.

[2] C. De Dobbelaere, J. Mullens, A. Hardy, M. K. Van Bael, Thermochim. Acta 2011,

520, 121.

[3] H. J. Snaith, Energy Environ. Sci. 2012, 5, 6513.

[4] D. A. Shirley, Phys. Rev. B 1972, 5, 4709.

[5] J. J. Yeh, I. Lindau, At. Data Nucl. Data Tables 1985, 32, 1.

[6] M. P. Seah, Practical Surface Analysis - 2nd ed., John Wiley & Sons Ltd., 1990.

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