Supplementary Materials for

Organometallic-functionalized interfaces for highly efficient inverted perovskite

solar cells

Zhen Li et al.

Corresponding authors: Nicholas J. Long, n.long@imperial.ac.uk; Zonglong Zhu, zonglzhu@cityu.edu.hk

Science 376, 416 (2022)

DOI: 10.1126/science.abm8566

The PDF file includes:

Materials and Methods

Supplementary Text
Figs. S1 to S28
Tables S1 to S5
References
23 Materials and Methods
24 Materials
25 Cesium iodide (CsI), formamidinium iodide (FAI) and methylammonium bromide
26 (MABr) were purchased from Dysol (Australia). Lead iodide (PbI2), and lead bromide
27 (PbBr2) were purchased from TCI (Japan). C60, poly[bis(4-phenyl)(2,4,6-
28 trimethylphenyl) amine] (PTAA) (Mn 6,000-15,000), methylammonium chloride
29 (MACl) and bathocuproine (BCP, purity of 99.9%) were purchased from Xi’an Polymer
30 Light Technology Corporation (China). Copper(I) thiophene-2-carboxylate (CuTC)
31 was purchased from Sigma-Aldrich. The solvents, including dimethylformamide
32 (DMF), dimethyl sulfoxide (DMSO), isopropanol (IPA) and chlorobenzene (CB) were
33 purchased from J&K (China) and used as received. Acetonitrile (MeCN),
34 dichloromethane (DCM), and hexane were purchased from Sigma-Aldrich and used as
35 received. High purity silver was purchased from commercial sources. Glass substrates
36 patterned with indium tin oxide (ITO) (15 Ω sq-1) were received from Mishi Tech. Co.,
37 Ltd. (China).
38
39 Ferrocenyl-bis-thiophene-2-carboxylate (FcTc2) synthesis
40 A solution of 1,1′-diiodoferrocene (FcI2) (synthesized according to previous report
41 (29)) (0.70 g, 1.60 mmol), CuTC (1.2 g, 6.32 mmol) and 9,10- dihydroanthracene
42 (synthesized according to previous report (30)) (0.60 g, 3.33 mmol) in MeCN (30 ml)
43 was stirred at 80 oC for 2 days. After cooling to room temperature, DCM (50 ml) was
44 added and the green-blue reaction mixture was filtered over Celite. The solvent was
45 then removed, and the crude mixture was dissolved in hexane and passed through a pad
46 of silica (ca. 5 cm), with the desired product eluting in 50% DCM in hexane. After
47 solvent removal, FcTc2 was obtained as a yellow solid (0.17 g, 0.38 mmol, 24%). 1H
48 nuclear magnetic resonance (NMR) (400 MHz, CDCl3, 298 K): δ (ppm) 7.78 (dd, J =
49 3.7, 1.3 Hz, 2H, Thio-H), 7.56 (dd, J = 5.0, 1.3 Hz, 2H, Thio-H), 7.06 (dt, J = 5.0, 3.7
50 Hz, 2H, Thio-H), 4.68 (t, J = 2.0 Hz, 4H, (CpTc)m-H), 4.10 (t, J = 2.0 Hz, 4H, (CpTc)o-
51 H). 13C{1H} NMR (100 MHz, CDCl3, 298 K): δ (ppm) 160.3 (2C, C=O), 134.2 (2C,
52 ThioC-H), 133.3 (2C, ThioC-CO2Fc), 133.2 (2C, ThioC-H), 128.0 (2C, ThioC-H),
2
53 116.6 (2C, CpC-O), 64.8 (4C, (CpTc)o-C-H), 62.2 (4C, (CpTc)m-C-H). MS ES+: m/z
54 437.9677 ([M]+ Calc.: 437.9683).
55

56 Diphenylferrocene (FcPh2) synthesis

57 FcPh2 was synthesized following the literature procedure (31).
58

59 (FA0.98MA0.02)0.95Cs0.05Pb(I0.95Br0.02)3-based device fabrication

60 Glass/ITO substrates (15 Ω sq-1) were sequentially cleaned by sonication with
61 detergent, deionized water, acetone and isopropyl alcohol for 20 min, respectively. Then,
62 the glass/ITO substrates were dried at 100 °C in an oven, and then were treated with
63 oxygen plasma for 10 min and finally transferred into a N2-filled glovebox before use.
64 The PTAA solution was prepared with a concentration of 2.2 mg ml-1 in CB. The 35 μL
65 as-prepared PTAA solution was spin-coated onto the ITO substrates at 6000 rpm for 30
66 s and the substrates were subsequently annealed at 100 °C for 10 min. The 1.73 M
67 perovskite precursor solution was prepared by mixing CsI, FAI, MABr, PbI2 and PbBr2
68 in 1 ml DMF:DMSO (5:1/v:v) mixed solvent with a chemical formula of
69 (FA0.98MA0.02)0.95Cs0.05Pb(I0.95Br0.02)3, 5 mol% of excess PbI2 was needed to improve
70 the device performance. Then 15.5 mol% MACl was added to the perovskite precursor
71 solution and stirred for 2h. 60 μL perovskite solutions were spin-coated onto
72 glass/ITO/hole transporting layer (HTL) at 1000 rpm for 10 s, subsequently at 5000
73 rpm for 40 s. 250 μL CB was slowly dripped onto the center of film at 12 s before the
74 end of spin-coating. The as-prepared perovskite films were subsequently annealed on a
75 hotplate at 110 ℃ for 20 min.
76 For the FcTc2-based devices, FcTc2 powder was prepared and dissolved in CB at
77 a concentration of 1 mg ml-1. The as-prepared yellowish solution was stirred at room
78 temperature (20-25 ℃) until the solution became clear. The solution was then
79 transferred to a N2-filled glovebox before use. 100 μL of FcTc2 solution was spin-coated
80 on top of the as-prepared perovskite at 5000 rpm for 20 s, and then transferred to the
81 hotplate and annealed at 100 ℃ for 2 min. The spin-coating processes were all
82 conducted at room temperature (20-25 ℃) in a N2-filled glovebox with the contents of
3
 83 O2 and H2O < 10 ppm. Finally, 20 nm C60 at a rate of 0.5 Å s-1, 6 nm BCP a rate of 0.5
84 Å s-1 and 100 nm silver electrode a rate of 1.0 Å s-1 were thermally evaporated,
85 respectively, under high vacuum (< 4 × 10−6 Torr). The device area was defined and
86 characterized as 0.08 cm2 by metal shadow mask.
87

88 MAPbI3-based device fabrication

89 The procedures of ITO/Glass substrate cleaning, and HTL deposit are consistent
90 with (FA0.98MA0.02)0.95Cs0.05Pb(I0.95Br0.02)3-based device fabrication. The MAPbI3
91 precursor solution was prepared by mixing 1.55 M MAI, and 1.63 M PbI2 in 1 ml
92 DMF:DMSO (5:1/v:v) mixed solvent, and stirring for 2h before use. 60 μL perovskite
93 solutions were spin-coated onto glass/ITO/HTL at 2000 rpm for 10 s, subsequently at
94 6000 rpm for 30 s. 250 μL CB was slowly dripped onto the center of the film at 7 s
95 before the end of spin-coating. The as-prepared perovskite films were subsequently
96 annealed on a hotplate at 100 ℃ for 30 min. The procedures of FcTc2 interlayer
97 deposition and metal electrode evaporation follow the description of
98 (FA0.98MA0.02)0.95Cs0.05Pb(I0.95Br0.02)3-based device fabrication.
99

100 FAPbI3-based device fabrication

101 The procedures of ITO/Glass substrate cleaning, and HTL deposit are consistent
102 with (FA0.98MA0.02)0.95Cs0.05Pb(I0.95Br0.02)3-based device fabrication. The FAPbI3
103 precursor solution was prepared by mixing 2 M FAI, and 2.06 M PbI2 in 1 ml
104 DMF:DMSO (8:1/v:v) mixed solvent. Then 35 mol% of MACl was added to the
105 perovskite precursor solution and stirred for 2h. 60 μL perovskite solutions were spin-
106 coated onto glass/ITO/HTL at 6000 rpm for 40 s. 250 μL CB was slowly dripped onto
107 the center of the film at 25 s before the end of spin-coating. The as-prepared perovskite
108 films were subsequently annealed on a hotplate at 135 ℃ for 1 h. The procedures of
109 FcTc2 interlayer deposition and metal electrode evaporation follow the description of
110 (FA0.98MA0.02)0.95Cs0.05Pb(I0.95Br0.02)3-based device fabrication.
111

112 (FA0.85MA0.15)0.95Cs0.05Pb(I0.85Br0.15)3-based device fabrication

4
113 The procedures of ITO/Glass substrate cleaning, and HTL deposit are consistent
114 with (FA0.98MA0.02)0.95Cs0.05Pb(I0.95Br0.02)3-based device fabrication. The 1.5 M
115 perovskite precursor solution was prepared by mixing CsI, FAI, MABr, PbI2 and PbBr2
116 in 1 ml DMF:DMSO (5:1/v:v) mixed solvent with a chemical formula of
117 (FA0.85MA0.15)0.95Cs0.05Pb(I0.85Br0.15)3, 10 mol% of excess PbI2 was needed to improve
118 the device performance. 60 μL perovskite solutions were spin-coated onto
119 glass/ITO/HTL at 5000 rpm for 30 s. 250 μL CB was slowly dripped onto the center of
120 the film at 7 s before the end of spin-coating. The as-prepared perovskite films were
121 subsequently annealed on a hotplate at 100 ℃ for 30 min. The procedures of FcTc2
122 interlayer deposition and metal electrode evaporation follow the description of
123 (FA0.98MA0.02)0.95Cs0.05Pb(I0.95Br0.02)3-based device fabrication.
124

125 Stability tests

126 The long-term operational stability was conducted by applying the perovskite solar
127 cells (PSCs) under 1 sun equivalent LED lamp in a N2-filled glovebox (with the
128 contents of O2 and H2O <10 ppm) at room temperature (25 ℃). The PSCs were biased
129 at maximum-power-point (MPP) voltage and the power output was tracked by using a
130 multi-potentiostat (CHI1040C, CH Instruments, Inc.). During the MPP test, the current
131 density-voltage (J-V) curves of the devices were obtained every 12 h to get the proper
132 loads for the MPP. Heat stability was assessed by applying the PSCs on the hotplate
133 (HS 7, IKA) maintained at 85 ℃ in a N2-filled glovebox (with the contents of O2 and
134 H2O <10 ppm), the power conversion efficiency (PCE) evolutions of the devices were
135 obtained through the periodical J-V measurement. The water and oxygen stability tests
136 were carried out by applying the PSCs in ambient air (40-50% RH) without any light
137 illumination, and the PCE evolutions of the devices were obtained through the
138 periodical J-V measurement.
139 For the stability tests following the IEC61215:2016 standard, the PSCs were
140 encapsulated by polyisobutylene (PIB) based polymer (PVS 101®) and covered with
141 1.1-mm glass sheets on both sides of the devices. The damp heat test was conducted by
142 keeping the encapsulated devices at 85 ℃/85% RH in the environment test chamber
5
143 (EL-10KA, ESPEC, Japan) for 1000 h. For the temperature cycling tests, the PSCs were
144 placed in the environment test chamber (EL-04KA, ESPEC, Japan), with the
145 temperature cycling between -40±2 ℃ to 85±2 ℃. The temperature change rate
146 between the -40 ℃ and 85 ℃ was set to not exceed 100 °C/h, and the temperature was
147 stable for at least 15 min at the temperature point of -40 ℃ and 85 ℃, respectively. The
148 encapsulated devices were measured periodically in an N2-filled glove box after the
149 devices cooling down.
150

151 Characterizations
152 X-ray diffraction (XRD) data were collected in the reflection mode at room
153 temperature on a Philips X’Pert diffractometer equipped with a CPS 180 detector using
154 monochromated Cu-Kα (λ = 1.5418 A) radiation. The surface and cross-section
155 morphology of the perovskite films were acquired by scanning electron microscopy
156 (SEM) (QUATTROS, Thermal Fisher Scientific). X-ray photo-electron spectroscopy
157 (XPS) measurements were conducted by AXIS Supra XPS system. Kelvin probe force
158 microscopy (KPFM) data were acquired via Bruker Dimension Kelvin probe force
159 microscopy in Potential Channel equipped with PFQNE-AL probe. Peak force infrared
160 (PFIR) measurements were carried out by a commercial Bruker NanoIR2-FS setup
161 (testing range from 900 to 1800 cm-1) consisting of an atomic force microscopy (AFM)
162 microscope operating in contact mode. Fourier-transform infrared (FTIR) spectroscopy
163 was conducted by Fourier transform infrared spectrometer (Tensor 27, Germany
164 Bruker). The steady-state and time-resolved photoluminescence (PL) spectra were
165 obtained by Edinburgh FLS980 applied with an excitation wavelength of 485 nm. The
166 film thickness of perovskite obtained by DektakXT stylus profiler. Ultraviolet-visible
167 (UV-vis) absorptions were measured by a UV-vis spectrometer (PerkinElmermodel
168 Lambda 2S). Time-of-flight secondary-ion mass spectrometry (Tof-SIMS)
169 measurements were performed using a TOF-SIMS V instrument (IONTOF GmbH,
170 Cameca IMS 4F).
171 The J-V characteristics of photovoltaic devices were conducted in a N2-filled
172 glovebox at room temperature by using a Xenon lamp solar simulator (Enlitech, SS-F5,
6
173 Taiwan). The power of the light was calibrated to 100 mW cm-2 by a silicon reference
174 cell (with a KG2 filter). Before J-V measurements, a 120-nm thick magnesium fluoride
175 layer was deposited on the back of ITO substrate for transmittance enhancement. All
176 the devices were measured using a Keithley 2400 source meter under a sweep mode of
177 reverse scan (from 1.20 V to -0.01 V) and forward scan (from -0.01 V to 1.20 V) with
178 the scan rate of 0.01 V s-1, and the delay time was 10 ms. No pre-conditioning was
179 needed before measurement. The stabilized power output was conducted by monitoring
180 the stabilized current density output at the MPP bias (extracted from the reverse scan J-
181 V curves). External quantum efficiency (EQE) measurements were carried out using a
182 QE-R EQE system (Enlitech, Taiwan). Highly sensitive EQE was measured by an
183 integrated system (PECT-600, Enlitech, Taiwan), where the photocurrent was amplified
184 and modulated by a lock-in instrument. Electroluminescence (EL) quantum efficiency
185 (EQEEL) was conducted by applying external voltage/current sources through the
186 instrument (ELCT-3010, Enlitech, Taiwan).
1 13
187 H and C{1H} NMR spectra were recorded on a Bruker Avance 400 MHz
188 spectrometer and referenced to the residual solvent peaks of either CDCl3 at 7.26 and
189 77.2 ppm or CD2Cl2 at 5.32 or 54.0 ppm, respectively. 1H-NMR spectra were fully
190 assigned using 2D correlation spectroscopy. Coupling constants are measured in Hz.
191 Mass spectrometry analyses were conducted by Dr. Lisa Haigh of the Mass
192 Spectrometry Service, Imperial College London.
193

194 Density functional theory (DFT) calculations

195 DFT calculations based on ab initio molecular dynamics were performed to
196 evaluate the interaction between FcTc2 and the (001) PbI2-terminated perovskite surface
197 using the Vienna Ab initio Simulation Package (version 5.4.4) with projector-
198 augmented-wave (PAW) pseudopotentials and PBE functional (32, 33). The energy cut-
199 off for plane waves of the Kohn-Sham states was set at 400 eV. Molecular dynamic
200 (MD) simulation was performed within the canonical ensemble NVT under a constant
201 temperature of 300 K. The time step was 2 fs and the gamma point was applied to
202 sample the Brillouin zone. Each trajectory was extracted every 50 fs until 100 ps after
7
203 thermal equilibrium. The optimization of the ground-state geometry for the FcTc2
204 molecule was performed with B3LYP functional and 6-31g(d,p) basis set using
205 Gaussian16 package (34). The analysis of electrostatic potential (ESP) was performed
206 within Multiwfn program (35, 36). The isosurface of van der Waals (vdW) surface was
207 set as 0.001 e/bohr3.
208
209
210

8
211 Supplementary Text
212 Peak Force Infrared Measurements
213 For PFIR imaging, the AFM operated under the peak force tapping mode, allowing
214 for the tip-sample distance to be known during the operation. During IR image
215 acquisition, where the IR source wavelength was fixed and the AFM tip was scanned
216 across the sample surface, chemical mapping of high spatial resolution was created,
217 while providing high-quality IR spectroscopy and chemical imaging for the organic
218 components in the perovskite films. The phase-locked loop synchronized the laser pulse
219 with each peak force tapping cycle. The four-quadrant photodiode read and digitized
220 the vertical deflection produced by laser-induced contact resonance. The PFIR signal
221 was obtained from the amplitude of the fast Fourier transform of the contact resonance.
222 For PFIR images, the scan area was 10×10 μm2, and the scan rate was 0.5 Hz. The
223 resonant frequency of the AFM tip was 264 kHz. Laser output power was dependent on
224 the selected frequency.
225

226 Space charge limited current (SCLC) measurements

227 Defect density calculations: The hole-only devices with the configurations of
228 ITO/PTAA/perovskite/Spiro-OMeTAD/MoO3/Ag and
229 ITO/PTAA/perovskite/FcTc2/Spiro-OMeTAD/MoO3/Ag were prepared to calculate the
230 defect density (N). In the SCLC regime, the current is dominated by charge carriers
231 injected from the contacts and the current-voltage characteristics become quadratic (I ~
232 V2). Fig. S12 shows the J-V curves of the fabricated devices on a double logarithmic
233 scale, which comprises the Ohmic region, the trap-filling limit (TFL) region and the
234 Child region. In the TFL region, the trap-state density (Nt) can be calculated by the

235 following equation：

2𝜀𝜀0 𝑉𝑇𝐹𝐿
236 𝑁𝑡 = (S1)
𝑞𝐿2

237 where ε and ε0 are the relative dielectric constant and vacuum permittivity, respectively.
238 VTFL is the onset voltage of TFL region, q is elementary charge. L represents perovskite
239 thin film thickness, which was calculated to 722 nm (Fig. S11). Therefore, the Nt can
9
240 be calculated to 1.71×1015 and 7.14×1014 cm−3 for the control device and device with
241 FcTc2, respectively.
242 Carrier mobility calculation: The electron-only devices with the configurations of
243 ITO/TiO2/perovskite/FcTc2/C60/BCP/Ag and ITO/TiO2/perovskite/C60/BCP/Ag were
244 fabricated to calculate the electron mobilities. As shown in Fig. S8, the J-V curve can
245 be defined as three regions, which are Ohmic region (n=1), trap-filled region and the
246 Child region (n=2). n represents the slope of linear region. The carrier mobility can be
9𝜀𝜀0 𝜇𝑉 2
247 calculated by fitting the child region to the Mott-Gurney law: 𝐽 = (S2), where
8𝐿3

248 ε and ε0 are the relative dielectric constant and vacuum permittivity, respectively. 𝜇 is
249 the carrier mobility, V is the onset voltage of TFL region, L represents perovskite thin
250 film thickness.
251

252 Photovoltage loss (VOC,loss) calculation

253 The detailed VOC,loss can be described by the equation listed below:
254 𝑞∆𝑉 = 𝐸𝑔 − 𝑞𝑉𝑂𝐶
𝑆𝑄 𝑆𝑄 𝑟𝑎𝑑 𝑟𝑎𝑑
255 = (𝐸𝑔 − 𝑞𝑉𝑂𝐶 ) + (𝑞𝑉𝑂𝐶 − 𝑞𝑉𝑂𝐶 ) + (𝑞𝑉𝑂𝐶 − 𝑞𝑉𝑂𝐶 )

𝑆𝑄 𝑆𝑄 𝑟𝑎𝑑 𝑛𝑜𝑛−𝑟𝑎𝑑
256 = (𝐸𝑔 − 𝑞𝑉𝑂𝐶 + 𝑞∆𝑉𝑂𝐶 ) + ∆𝑞𝑉𝑂𝐶 + ∆𝑞𝑉𝑂𝐶

257 = 𝑞(∆𝑉1 + ∆𝑉2 + ∆𝑉3 ) (S3)

258 where q, ∆V, Eg is the elementary charge, the total voltage loss, and the bandgap of
259 perovskite, respectively. VOCSQ is the Shockley-Queisser limit of open circuit voltage,
260 VOCrad is the VOC without non-radiative recombination occurring in PSCs, ∆VOCSQ is the
261 VOC loss due to the non-ideal EQE above the bandgap, ∆VOCrad is the VOC loss due to
262 the sub-bandgap radiative recombination, and ∆ VOCnon-rad is the VOC loss of non-
263 radiative recombination. As a consequence, the energy loss can be divided into three
264 parts, ΔV1, ΔV2 and ΔV3, which represent radiative recombination above Eg, energy loss
265 from blackbody radiation and voltage loss induced by the nonradiative recombination,
266 respectively.

10
267 The photovoltaic bandgap (Eg, PV) of 1.548 eV can be obtained from the inflection
268 point of the EQE spectra by locating the maximum point (𝜆𝑔 ) of the Gaussian-like

269 derivate 𝜕𝐸𝑄𝐸/𝜕𝜆 (37) (Fig. S25). Eg, PV was defined as the mean peak energy at the
270 absorption edge of the distribution, and it should be considered as a convention for the
271 determination of bandgap energy to any solar cells. Since it represents an external
272 property of a photovoltaic device and not an internal property of a photovoltaic material
273 (e.g. extracted from the Tauc plot), it is more precise to estimate a bandgap for a solar
274 cell device (38).
275 According to a previous report (39), the VOC of a solar cell can be calculated by
276 the equation:
𝑘𝐵 𝑇 𝐽
277 𝑉𝑂𝐶 = 𝑞
ln ( 𝐽𝑆𝐶 ) (S5)
0

278 where 𝑞 , 𝑘𝐵 , 𝑇 , JSC, J0, represents the element charge, Boltzmann constant,
279 temperature, short-circuit current, and dark saturation current, respectively. The JSC and
280 J0 can be described as:
∞
281 𝐽𝑆𝐶 = 𝑞 ∫0 𝐸𝑄𝐸𝑃𝑉 (𝐸)𝜙𝐴𝑀1.5 (𝐸) 𝑑𝐸 (S6)
𝑞 ∞
282 𝐽0 = 𝐸𝑄𝐸 ∫0 𝐸𝑄𝐸𝑃𝑉 (𝐸)𝜙𝐵𝐵 (𝐸) 𝑑𝐸 (S7)
𝐸𝐿

2𝜋𝐸 2 1
283 𝜙𝐵𝐵 (𝐸) = (S8)
ℎ3 𝑐 2 exp(
𝐸
)−1
𝑘𝐵 𝑇

284 where 𝐸𝑄𝐸𝑃𝑉 , 𝐸𝑄𝐸𝐸𝐿 is photovoltaic external quantum efficiency and

285 electroluminescence external quantum efficiency, respectively. 𝜙𝐴𝑀1.5, 𝜙𝐵𝐵 is solar
286 cell radiative spectrum and black-body radiative spectrum, respectively. 𝑐 is light
287 speed in vacuum.
288 According to the Schokley-Queisser limit (S-Q limit): (1) The 𝐸𝑄𝐸𝑃𝑉 is
1, 𝐸 ≥ 𝐸𝑔
289 described with Heaviside step function, where 𝐸𝑄𝐸𝑃𝑉 (𝐸) = { ; (2) only the
0, 𝐸 < 𝐸𝑔
290 photons with energy larger than bandgap (𝐸𝑔 ) are absorbed; (3) all recombination is

291 radiative (𝐸𝑄𝐸𝐸𝐿 = 1). Therefore, JSC and J0 in S-Q limit can be written as:
𝑆𝑄 ∞
292 𝐽𝑆𝐶 = 𝑞 ∫𝐸 𝜙𝐴𝑀1.5 (𝐸) 𝑑𝐸 (S9)
𝑔

∞
293 𝐽0𝑆𝑄 = 𝑞 ∫𝐸 𝜙𝐵𝐵 (𝐸) 𝑑𝐸 (S10)
𝑔

11
294 Therefore, VOC in S-Q limit is:
𝑆𝑄
𝑆𝑄 𝑘𝐵 𝑇 𝐽
295 𝑉𝑂𝐶 = ln ( 𝑆𝐶
𝑆𝑄 ) (S11)
𝑞 𝐽0

𝑆𝑄
296 Considering the theory of S-Q limit, 𝑉𝑂𝐶 can be degraded to VOC with three

297 components of loss. The first VOC loss component is due to the non-ideal 𝐸𝑄𝐸𝑃𝑉 , which
298 is less than 100%. In this situation, short-circuit current is expressed as:
∞
299 𝐽𝑆𝐶 = 𝑞 ∫0 𝐸𝑄𝐸𝑃𝑉 (𝐸)𝜙𝐴𝑀1.5 (𝐸) 𝑑𝐸 (S12)

𝑆𝑄
300 The ∆𝑉𝑂𝐶 was calculated as below:
𝑆𝑄
𝑆𝑄 𝑆𝑄 𝑘𝐵 𝑇 𝐽𝑆𝐶 𝑘𝐵 𝑇 𝐽
301 ∆𝑉𝑂𝐶 = 𝑉𝑂𝐶 − ln ( 𝑆𝑄 ) = ln ( 𝐽𝑆𝐶 ) (S13)
𝑞 𝐽0 𝑞 𝑆𝐶

302 The second VOC loss component originates from the energy loss related with extra
303 thermal radiation of solar cell in dark. The 𝐸𝑄𝐸𝑃𝑉 extends into the sub-bandgap region,
304 where the black-body radiation increases with the photo energy lowering. Thus, this
305 sub-bandgap 𝐸𝑄𝐸𝑃𝑉 increased the dark saturation current. The short-circuit
𝑟𝑎𝑑
306 current 𝐽𝑆𝐶 is equal to 𝐽𝑆𝐶 , and dark saturation current in this condition are written as:
∞
307 𝐽0𝑟𝑎𝑑 = 𝑞 ∫0 𝐸𝑄𝐸𝑃𝑉 (𝐸)𝜙𝐵𝐵 (𝐸) 𝑑𝐸 (S14)
𝑟𝑎𝑑
308 therefore, the radiative VOC loss, ∆𝑉𝑂𝐶 , is:
𝑟𝑎𝑑 𝑘𝐵 𝑇 𝐽𝑆𝐶 𝑘𝐵 𝑇 𝑆𝐶𝐽 𝑘𝐵 𝑇 𝐽𝑟𝑎𝑑
309 ∆𝑉𝑂𝐶 = ln (𝑆𝑄 )− ln (𝐽𝑟𝑎𝑑 )= ln ( 0𝑆𝑄 ) (S15)
𝑞 𝐽0 𝑞 0 𝑞 𝐽0
𝑛𝑜𝑛𝑟𝑎𝑑
310 The third VOC loss component, ∆𝑉𝑂𝐶 , which is attributed to the non-radiative
311 recombination in the device, can be calculated as:
𝑛𝑜𝑛𝑟𝑎𝑑 𝑘𝐵 𝑇 𝐽𝑆𝐶
312 ∆𝑉𝑂𝐶 = ln ( ) − 𝑉𝑂𝐶 (S16)
𝑞 𝐽0𝑟𝑎𝑑

313 According to Equation S6 and S13, 𝐽0rad = EQEEL ⋅ 𝐽0 , so combining Equation S4,
314 Equation S17 can be rewritten as:
nonrad
𝑘B 𝑇 𝐽SC 𝑘B 𝑇 𝐽SC
315 ∆𝑉OC = ln ( )− ln ( )
𝑞 EQEEL ⋅ 𝐽0 𝑞 𝐽0
𝑘B 𝑇
316 =− ln(EQEEL )
𝑞

317 The PSCs with and without FcTc2 show similar ΔV1 of ~274 mV. As the EQE of
318 the device protrudes into the area below Eg and brings about more black-body radiation,
319 we characterized the highly-sensitive EQE below bandgap to calculate ∆V2 (Fig. S26).

12
320 The calculated ∆V2 is 20.67 mV and 31.50 mV for the FcTc2-based and control devices,
321 respectively. ΔV3 is the VOC loss from the non-radiative recombination, which can be
322 deduced using the equation S22, where EQEEL is the EQE of electroluminescence (EL).
323 The ΔV3 of control PSC and PSC incorporated with FcTc2 can be calculated to 108.57
324 and 68.75 mV, respectively.

13
325
326 Fig. S1. UV-vis absorption spectrum of FcTc2 dissolved in chlorobenzene.
327

14
328
329 Fig. S2. UV-vis absorption spectrum of FcTc2 thin film spin-coated on glass substrate.
330

15
331
332 Fig. S3. Cross-section SEM image of fabricated inverted PSC with a structure of
333 ITO/PTAA/perovskite/FcTc2/C60/BCP/Ag.
334

16
335
336 Fig. S4. XRD patterns of FcTc2, pristine perovskite film, and perovskite thin films
337 modified with different concentrations of FcTc2 (0.5, 1.0 and 2.0 mg ml-1).
338

17
339

340
341 Fig. S5. SEM images of pristine perovskite film and perovskite films modified with
342 different concentrations of FcTc2 (0.5, 1.0 and 2.0 mg ml-1).
343

18
344
345 Fig. S6. UV-vis absorption spectra of pristine perovskite film, and perovskite films with
346 different concentrations of FcTc2 incorporation (0.5, 1.0 and 2.0 mg ml-1).
347

19
348

349
350 Fig. S7. Electrostatic potential (ESP) analysis of FcTc2, in which the electronegativity
351 of O, S and H atoms is -29.79 kcal mol-1, -8.12 kcal mol-1 and 15.16 kcal mol-1,
352 respectively. The high electronegativity of O drives the formation of stable Pb-O bonds
353 and significantly enhances the electrostatic attraction between the perovskite and FcTc2
354 interface.
355

20
356

357
358 Fig. S8. SCLC plots of perovskite films (A) with and (B) without FcTc2 based on an
359 electron-only device (ITO/TiO2/perovskite/C60/BCP/Ag).
360

21
361

362

363 Fig. S9. TRPL spectra of perovskite/FcTc2/C60 and perovskite/C60.

364

22
 Pristine 799 nm
0.5 mg mL-1
804 nm
PL Intensity (a.u.)
1.0 mg mL-1
2.0 mg mL-1

700 800 900

Wavelength (nm)
365
366 Fig. S10. Steady-state PL spectra of pristine perovskite film and perovskite films with
367 different concentrations of FcTc2 (0.5, 1.0 and 2.0 mg ml-1) excited via a laser with the
368 wavelength of 485 nm.
369

23
370
371 Fig. S11. The film thickness of perovskite obtained by DektakXT stylus profiler. The
372 film thickness of perovskite is therefore calculated to be 722 nm.
373
374

24
375
376 Fig. S12. SCLC plots of perovskite films (A) with and (B) without FcTc2 based on a
377 hole-only device (ITO/PTAA/perovskite/Spiro-OMeTAD/MoO3/Ag).
378

379

380

25
381

382 Fig. S13. FTIR characterization of FAPbI3, MAPbI3, and FcTc2-modified CsFAMA
383 perovskite films before and after heating.
384

26
385

386 Fig. S14. XRD pattern of the pristine perovskite film and perovskite film treated by
387 FcTc2 before and after 200 h heat/light aging, respectively.
388

389
390

27
391

392
393 Fig. S15. PFIR microscopy at an IR frequency of 1480 cm–1 (which is resonant with
394 the C-N stretching absorption of MA+ ion) of FcTc2-modified perovskite films (A) and
395 control (B) after heating (continues 85 ℃) treatment for 1000 hours.
396

28
397
398 Fig. S16. PFIR microscopy at an IR frequency of 1480 cm–1 (which is resonant with
399 the C–N stretching absorption of MA+ ion) of FcTc2-modified perovskite films (A) and
400 control (B) after 1-sun illumination treatment for 1000 hours.
401

29
402
403 Fig. S17. Photovoltaic performance of the best performing control devices and devices
404 with different concentrations of FcTc2 (0.5, 1.0 and 2.0 mg ml-1). The photovoltaic
405 parameters are summarized in Table S2.
406

30
407
408 Fig. S18. Statistics of key photovoltaic parameters (open-circuit voltage (VOC), fill
409 factor (FF), short-circuit current density (JSC), PCE) obtained from the J-V
410 characteristic of 20 control devices, and devices modified with different concentrations
411 of FcTc2 (0.5, 1.0 and 2.0 mg ml-1). The average value and standard deviation of each
412 parameter is summarized in Table S2.
413
414
415

31
416
417 Fig. S19. J-V curve of the best performing FcTc2-based device under reverse and
418 forward scans.
419
420

32
421
422 Fig. S20. Independent efficiency certification of perovskite solar cells by an accredited
423 institute of National Institute of Metrology (NIM, China), giving a PCE of 24.3%
424 (short-circuit current (ISC) of 2.077 mA, VOC of 1.179 V and FF of 80.6%, reverse scan),
425 which is among the highest values of the certified efficiency for inverted perovskite
426 solar cells.
427
428

33
429

430
431 Fig. S21. (A) J-V curves of the best performing MAPbI3-based PSCs with and without
432 FcTc2, respectively. The photovoltaic parameters are summarized in Table S4. (B)
433 Histograms of the PCE values among 20 devices of MAPbI3-based PSCs with and
434 without FcTc2, respectively.
435

34
436
437 Fig. S22. (A) J-V curves of the best performing PSCs of
438 (FA0.85MA0.15)0.95Cs0.05Pb(I0.85Br0.15)3-based PSCs with and without FcTc2, respectively.
439 The photovoltaic parameters are summarized in Table S4. (B) Histograms of the PCE
440 values among 20 devices of (FA0.85MA0.15)0.95Cs0.05Pb(I0.85Br0.15)3-based PSCs with and
441 without FcTc2, respectively.
442

35
443
444 Fig. S23. (A) J-V curves of the best performing PSCs of FAPbI3-based PSCs with and
445 without FcTc2, respectively. The photovoltaic parameters are summarized in Table S4.
446 (B) Histograms of the PCE values among 20 devices of FAPbI3-based PSCs with and
447 without FcTc2, respectively.
448

36
449
450 Fig. S24. J-V curve and photovoltaic performance of the PSCs treated with ferrocene-
451 based control diphenylferrocene (FcPh2), inset is the molecular structure of FcPh2.
452

37
453
454 Fig. S25. Eg, PV estimation obtained from the inflection point of the EQE spectra by
455 locating the maximum point (𝜆𝑔 ) of the Gaussian-like derivate 𝜕𝐸𝑄𝐸/𝜕𝜆.
456

38
 100

10-1
EQE

10-2

10-3
Control
FcTc2
10-4
1.25 1.30 1.35 1.40 1.45 1.50 1.55 1.60 1.65 1.70
Photon Energy (eV)
457
458 Fig. S26. Highly sensitive EQE of control PSCs and FcTc2-based PSC.
459

39
460

461
462 Fig. S27. Stability test based on unencapsulated devices with and without FcTc2 under
463 continuous heating at 85 °C in a N2 atmosphere.
464
465

40
466

467
468 Fig. S28. Stability test based on unencapsulated devices with and without FcTc2 stored
469 in ambient air (40-50% RH, 25 ℃) in the dark.
470

41
471 Table S1. The fitted carrier lifetime of perovskite films obtained from the TRPL
472 measurements (refer to Fig. 2C).

τ1 (ns) τ2 (ns) τave (ns)

Control 98.11 1173.63 1166.74

FcTc2 440.22 2187.88 2159.22

Note: The average lifetime can be calculated with the equation of: 𝜏𝑎𝑣𝑔 = (𝐴1 𝜏12 +

𝐴2 𝜏22 )/(𝐴1 𝜏1 + 𝐴2 𝜏2 ), where parameters A1 and A2 are the amplitude fraction for
each decay component, and 𝜏1 and 𝜏2 represent the time constant of the two types
of decay.
473

474

42
475 Table S2. Summary of key photovoltaic parameters of PSCs and PSCs incorporated
476 with different concentrations of FcTc2 (extracted from Figs. S17 and S18).

VOC (V) JSC (mA cm-2) FF (%) PCE (%)

1.130±0.011 24.95±0.40 79.89±0.81 22.5±0.4

Control
(1.133) (25.25) (80.45) (23.0)
1.138±0.011 24.93±0.50 79.72±1.24 22.6±0.5
0.5 mg ml-1
(1.143) (25.33) (80.48) (23.3)
1.178±0.007 25.40±0.20 81.80±1.09 24.5±0.4
1.0 mg ml-1
(1.184) (25.68) (82.32) (25.0)
1.150±0.013 25.62±0.28 77.03±1.14 21.8±0.4
2.0 mg ml-1
(1.146) (24.82) (78.84) (22.4)
Note: The parameters listed in parentheses are the best performing devices (refer to
Fig. S17). The plus-minus sign (±) represents the standard deviation.
477
478

43
479 Table S3. Summary of high-performance p-i-n structure perovskite solar cells.

Certified
Year Strategy Reference
Efficiency

Novel inorganic
2015 charge extraction 15.0% (40)
layer

Perovskite-fullerene
2016 graded heterojunction 18.2% (41)
engineering

Quaternary
ammonium halides
2017 20.6% (42)
for defects
passivation

Solution-processed
2018 secondary growth 20.9% (14)
technique

Novel electron-
2020 21.3% (9)
extraction layer

Managing grains and

2020 interfaces via ligand 22.3% (8)
anchoring

Novel molecule
2020 designed for defects 22.8% (16)
passivation

Perovskite precursor
2021 22.6% (43)
engineering

Perovskite surface
2022 23.5% (44)
modification

Interfacial modulation
by organometallic-
2022 24.3% This work
functionalized
interfaces

Note: the “p-i-n” structure device was defined as the hole collected at the bottom
transparent conducting oxide electrode.

480
44
481 Table S4. The photovoltaic parameters of the best performing devices of MAPbI3 (refer
482 to Fig. S21A), (FA0.85MA0.15)0.95Cs0.05Pb(I0.85Br0.15)3 (refer to Fig. S22A), FAPbI3 (refer
483 to Fig. S23A) perovskites with and without FcTc2.

JSC
VOC FF PCE Average
Device (mA
(V) (%) (%) PCE (%)
cm-2)

MAPbI3 1.058 80.12 23.08 19.6 18.1

MAPbI3-FcTc2 1.137 80.80 23.26 21.4 20.7

(FA0.85MA0.15)0.95Cs0.05Pb(I0.85Br0.15)3 1.091 82.00 22.61 20.2 19.6

(FA0.85MA0.15)0.95Cs0.05Pb(I0.85Br0.15)3-
1.176 81.37 22.76 21.8 21.0
FcTc2

FAPbI3 1.033 79.40 25.36 20.8 20.1

FAPbI3-FcTc2 1.095 81.23 25.38 22.6 21.4

484
485

45
486 Table S5. Results of calculated VOC loss in the control PSCs and FcTc2-based PSCs.

Device Eg,PV VOC,SQ VOC ΔV1 ΔV2 ΔV3 VOC,loss VOC*

(eV) (V) (V) (mV) (mV) (mV) (mV) (V)
Control 1.548 1.276 1.133 274.07 31.50 108.57 414.14 1.134

FcTc2 1.548 1.276 1.184 273.63 20.67 68.75 363.05 1.185

VOC is the value extracted from J-V curve

VOC* is the value based on the Eg,PV and VOC,loss

487
488

46
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