Articles

https://doi.org/10.1038/s41560-022-01038-1

In situ growth of graphene on both sides of a

Cu–Ni alloy electrode for perovskite solar cells
with improved stability
Xuesong Lin   1,7, Hongzhen Su1,7, Sifan He2,7, Yenan Song   2,7, Yanbo Wang   1 ✉, Zhenzhen Qin1,
Yongzhen Wu3, Xudong Yang   1, Qifeng Han1, Junfeng Fang2, Yiqiang Zhang   4, Hiroshi Segawa5,
Michael Grätzel   6 and Liyuan Han   1,4,5 ✉

The instability of rear electrodes undermines the long-term operational durability of efficient perovskite solar cells. Here,
a composite electrode of copper–nickel (Cu–Ni) alloy stabilized by in situ grown bifacial graphene is designed. The alloying
makes the work function of Cu suitable for regular perovskite solar cells. Cu–Ni is the ideal substrate for preparing high-quality
graphene via chemical vapour deposition, which simultaneously protects the device from oxygen, water and reactions between
internal components. To rivet the composite electrode with the semi-device, a thermoplastic copolymer is applied as an
adhesive layer through hot pressing. The resulting devices achieve power conversion efficiencies of 24.34% and 20.76%
(certified 20.86%) with aperture areas of 0.09 and 1.02 cm2, respectively. The devices show improved stability: 97% of their
initial efficiency is retained after 1,440 hours of a damp-heat test at 85 °C with a relative humidity of 85%; 95% of their initial
efficiency is retained after 5,000 hours at maximum power point tracking under continuous 1 sun illumination.

M
etal halide perovskite solar cells (PSCs) have attracted or polymers is hard21; thus, increased intrinsic chemical stability of
great attention in both academia and industry owing to rear electrodes for PSCs is needed.
their excellent optoelectronic performance and low man- Copper (Cu) is a potential candidate due to its relative inertness
ufacturing costs1–6. However, for PSCs to realize commercializa- to migrated perovskite components, and it has been widely used in
tion, they must survive the long-term natural erosion imposed by inverted PSCs22. However, its work function (WF) of 4.65 eV limits its
oxygen, moisture, light and heat7,8. Thanks to the optimization of application in efficient regular PSCs, which usually use 2,2′,7,7′-tet
the perovskite materials, charge transport materials and interface rakis(N,N-dip-methoxyphenylamine)-9,9′-spirobifluorene
layers9–12, the operational stability of PSCs has made great progress; (spiro-MeOTAD) or poly(bis(4-phenyl)(2,4,6-trimethylphenyl)
but one of the key functional layers, the rear electrode, is still prone amine) (PTAA) with a highest occupied molecular orbital (HOMO)
to fail, which limits the overall durability of efficient PSCs13,14. of around −5.2 eV (ref. 23). In addition, Cu can be oxidized by oxy-
Silver (Ag) and aluminium (Al) are commonly used rear elec- gen and moisture to generate products such as Cu2(OH)2CO3, and
trodes; however, they tend to react with migrated halide anions Cu atoms were reported to diffuse into perovskite at 85 °C (ref. 24). In
from perovskite to form resistive compounds such as AgI and addition to metal electrodes, intrinsically stable carbon electrodes
AlI3 (refs. 15–17). In the case of gold (Au), although the formation have also been applied to PSCs; 9,000 hours of operational stability
enthalpy of Au–I is much higher than those of Ag–I or Al–I, Au at the maximum power point (MPP) and 55 °C was recently reported
atoms can diffuse into the perovskite to form antisite defects of AuPb with no obvious change in the power conversion efficiency (PCE)25.
with deep level, which act as efficient non-radiative recombination However, big challenges exist for carbon electrodes to obtain high
centres18. In addition, the use of noble metals comes at a high price efficiencies because of the severe potential losses26. Therefore, it is
and implies more stringent requirements for vacuum and tem- still an open issue to develop a low-cost rear electrode with a tunable
perature, which will significantly increase the manufacturing costs. WF that combines chemical stability and high efficiency.
To suppress the interaction between perovskite and metal atoms, Herein, we report a composite electrode that consists of (1) cop-
introducing a thin buffer layer to separate them without hindering per–nickel (Cu–Ni) alloy and (2) in situ grown bifacial graphene.
the charge transport has been reported as a successful strategy19,20. The alloying of Cu with Ni improves its electrochemical stability
However, materials from the perovskite or the electrode tend to without compromising the electrical properties and makes it pos-
penetrate that buffer layer on a long timescale because achieving a sible to tune the WF of Cu to fit the requirements of regular PSCs
thin but uniform, compact coverage on a large area with buffer lay- by simply varying the content of Ni. Moreover, Cu–Ni alloy is an
ers that are usually formed by solution-processable small molecules ideal substrate for preparing high-quality graphene on both sides

1
State Key Laboratory of Metal Matrix Composites, Shanghai Jiao Tong University, Shanghai, China. 2Engineering Research Center for Nanophotonics and
Advanced Instrument, Ministry of Education, School of Physics and Electronic Science, East China Normal University, Shanghai, China. 3Key Laboratory
for Advanced Materials and Institute of Fine Chemicals, School of Chemistry and Molecular Engineering, East China University of Science and Technology,
Shanghai, China. 4School of Materials Science and Engineering, Henan Institute of Advanced Technology, Zhengzhou University, Zhengzhou, China.
5
Special Division of Environmental and Energy Science, Komaba Organization for Educational Excellence, College of Arts and Sciences, University of
Tokyo, Tokyo, Japan. 6Laboratory of Photonics and Interfaces, Institute of Chemical Sciences and Engineering, École Polytechnique Fédérale de Lausanne
(EPFL), Lausanne, Switzerland. 7These authors contributed equally: Xuesong Lin, Hongzhen Su, Sifan He, Yenan Song. ✉e-mail: sjtu-wyb@sjtu.edu.cn;
han.liyuan@sjtu.edu.cn

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Nature Energy Articles
a b c mapping images confirm the uniform distribution of Ni in the
Cu foil (Supplementary Fig. 2f,g) after thermal annealing under a
reducing atmosphere, and the semiquantitative stoichiometry of the
Cu–Ni alloy is 81:19 (Cu/Ni). The exact stoichiometry of the Cu–Ni
alloy is measured by an inductively coupled plasma spectrometer,
and the result of 83.537:16.463 (Cu/Ni) is close to that measured
20 µm 20 µm 20 µm by EDS. The process of thermal annealing under a reducing atmo-
sphere also smoothes the surface of the substrate, thereby preparing
d 75
e 75
f 75
it for the in situ growth of graphene, as demonstrated by atomic
force microscopy (AFM; Supplementary Fig. 2h).
A uniform but thin layer of graphene is required to meet the
demand of being an efficient barrier without introducing extra
defects or hindering the carrier transport27. We focus on the char-
acterization of one side since the quality of graphene on both sides
20 µm 20 µm 20 µm should be identical in a CVD method. Using CH4 as the carbon
20 20 20 source, with respective flow rates of 5, 10 and 15 standard cubic cen-
g h i timetres per minute (sccm), diluted in 100 sccm Ar/H2, we arm both
5 5 5 sides of the Cu–Ni alloy with graphene with varying numbers of lay-
ers and quality, denoted as CNG-5, CNG-10 and CNG-15, respec-
tively. Their optical microscope images are provided in Fig. 1a–c.
Obviously, due to the differences in the content of the carbon source,
the graphene layers on CNG-5 and CNG-15 form a non-uniform
monolayer and a coexisting monolayer and bilayer, respectively. By
20 µm 20 µm 20 µm
contrast, a uniform monolayer graphene is observed on CNG-10.
0 0 0
To further determine the quality and layer numbers of graphene,
Raman spectra are measured for the three samples. The full width at
Fig. 1 | The quality and number of layers of graphene of CNG composite
half maximum values for the 2D peak at ~2,680 cm−1 are shown in
electrodes characterized by optical microscope and Raman spectra.
Fig. 1d–f; the graphene of CNG-10 exhibits the most uniform distri-
a–c, Optical microscope images of graphene on CNG-5, CNG-10 and CNG-15,
bution of full width at half maximum for the 2D peak with an aver-
respectively. d–f, Raman mapping of 2D peak full width at half maximum of
age value of below 45 cm−1. Coupled with the intensity ratios of the
graphene on CNG-5, CNG-10 and CNG-15, respectively. The unit of the colour
2D peak and G peak at ~1,584 cm−1 (I2D/IG), as shown in Fig. 1g–i,
bar in d–f is per centimetre. g–i, The I2D/IG of graphene on CNG-5, CNG-10
the layer numbers of graphene on CNG-5, CNG-10 and CNG-
and CNG-15, respectively. The unit of the colour bar in g–i is dimensionless.
15 can be deduced28. The graphene of CNG-5 contains regions of
The transfer method of the graphene, used for the measurements with
I2D/IG > 2.5, which represents a discontinuous monolayer graphene
Raman spectra and the optical microscope, is based on previous work28.
film and is consistent with the optical microscope image in Fig. 1a.
The I2D/IG for CNG-10 almost resides between 1.5 and 2.5, indicat-
by chemical vapour deposition (CVD); this graphene acts as a natu- ing the formation of monolayer graphene. A further increase in the
ral barrier and substantially strengthens the stability of the Cu–Ni content of CH4 leads to blue regions for CNG-15 (0.8 < I2D/IG < 1.2),
alloy because the outer graphene can block the penetration of water which is indicative of the formation of a non-uniform bilayer and
and oxygen, while the inner graphene can suppress the migration agrees well with the full width at half maximum of 60 cm−1 in Fig. 1f.
of perovskite components or metal atoms caused by light and heat. Incomplete coverage may weaken the function of being the barrier
The composite electrode is hot-pressed on the semi-device with the for water, oxygen and migrated components, whereas overlapped
assistance of a thermoplastic copolymer, which ensures the efficient graphene not only enlarges the defect density at this interface
charge collection at the interface of the semi-device and the electrode. (Supplementary Fig. 3a–c) but also increases the series resistance
As a result, a PCE of 24.34% was achieved for the regular device using (RS) of PSCs. Therefore, CNG-10 is expected to be the most suitable
graphene/Cu–Ni/graphene composite as the rear electrode (the composite electrode among the three samples.
CNG device) with an aperture area of 0.09 cm2, comparable to that of
the device using a Ag electrode. After the optimization of the ther- Assembly and performance of CNG devices. Before the assembly
moplastic copolymer with a conductive graphene nanoflake (GN), of an integral device, we first demonstrate the high quality of the
we obtained a PCE of 20.76% (certified PCE, 20.86%) for the CNG perovskite film used in our work, which shows a microscale grain
device with an aperture area of 1.02 cm2. The CNG devices retained size (Supplementary Fig. 4a), with a thickness of ~650 nm (Fig. 2a).
97% of their initial PCEs after the aging test of heating at 85 °C with Featured peaks of α-NH2CHNH2PbI3 (α-FAPbI3) and PbI2 at 13.9°
a relative humidity of ~85% for 1,440 hours, and the encapsulated and 12.7°, respectively, are observed in X-ray diffraction patterns
devices maintained 95% of their initial PCEs after operating at the (Supplementary Fig. 4b), and the δ-FAPbI3 at 11.8° is suppressed.
MPP under continuous 1 sun illumination for 5,000 hours. The results from ultraviolet–visible (UV-vis) absorption spectroscopy
and photoluminescence show the absorption edge of our perovskite
Fabrication and characterization of CNG electrodes. The fab- at 820 nm (Supplementary Fig. 4c), which is equivalent to an optical
rication process of the CNG composite electrode and the assem- bandgap of 1.51 eV. Moreover, the time-resolved photoluminescence
bly of the whole device (Supplementary Fig. 1) are detailed in the result of the perovskite determined from the mono-exponential fitting
Methods. The thickness of the sputtered Ni before annealing is set at exhibits a long carrier lifetime of 2.50 μs (Supplementary Fig. 4d and
200 nm to obtain a WF for Cu–Ni (denoted as CN-2) that is compat- Supplementary Table 1). Then, we investigate the effect of graphene
ible with the HOMO of spiro-MeOTAD or PTAA (Supplementary on the WFs of the Cu–Ni alloy by ultraviolet photoelectron spectros-
Fig. 2a–d). As shown in the cross-sectional scanning electron copy. As shown in Supplementary Fig. 5a–d, the WFs of the CNG-5,
microscopy (SEM) image (Supplementary Fig. 2e), the thickness CNG-10 and CNG-15 composite electrodes are 5.15, 5.11 and 4.99 eV,
of Cu–Ni is approximately equal to that of Cu foil (~25 μm). The respectively, which are also compatible with the HOMOs of the com-
corresponding energy dispersive spectroscopy (EDS) elemental monly used hole transport materials (HTMs) in regular PSCs.

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Articles Nature Energy

a b 28

CNG electrode 24

20
EVA

JSC (mA cm–2)

Spiro-MeOTAD
16

Perovskite 12

8
SnO2
Ag
400 nm CNG-5
FTO 4
CNG-10
CNG-15
0
0 0.2 0.4 0.6 0.8 1.0 1.2
VOC (V)

c d 450
25
EVA–0.8 wt% GN
400 EVA–1.6 wt% GN
EVA–2.4 wt% GN
20
350
37.8 µs

Photovoltage (mV)
JSC (mA cm–2)

300
15 34.5 µs
250

10 200

150
5 EVA–0.8 wt% GN 20.1 µs
EVA–1.6 wt% GN 100
EVA–2.4 wt% GN
0 50
0 0.4 0.8 1.2 –100 0 100 200 300 400 500
VOC (V) Time (µs)

e f

140 140

120 120

100 100

80 80

60 60

40 40

20 20
10 µm 10 µm
0 0

Fig. 2 | The structure and performance of PSCs with aperture areas of 0.09 and 1.02 cm2. a, Cross-sectional SEM image of CNG-10 device. b, J–V curves
of CNG and Ag devices with an aperture area of 0.09 cm2 under forward scan. c,d, J–V curves (c) and corresponding transient photovoltage results (d) of
1.02 cm2 CNG devices with modified adhesive layers with different mass ratios of GN in EVA. e,f, Raman mapping of G peak for 1.6 wt% (e) and 2.4 wt%
(f) GN in EVA. The colour bars in e and f represent the intensity of the G peak with arbitrary units.

The integral devices are fabricated by hot pressing CNG elec- time are optimized to be 3 bar and 60 seconds, respectively, after
trodes on the semi-device with the structure of fluorine-doped the measurement of the resistance of the CNG electrodes/EVA/
tin oxide (FTO)/SnO2/perovskite/HTM. A thin adhesive layer spiro-MeOTAD/FTO (Supplementary Fig. 7a,b). It is also found
(~2.9 nm) of thermoplastic ethylene vinyl acetate (EVA) copo- that the resistance will increase when the time is over 120 seconds
lymer with a WF of 3.69 eV and a deep HOMO level of −7.48 eV (3 bar, 130 °C), while the pressure seems to have no obvious influ-
(Supplementary Fig. 6a–c) is employed at the interface to assist the ence on the sample resistance.
combination of HTMs and CNG electrodes and to fill the possible To further investigate the effect of time and pressure for hot
gaps left after hot pressing, which is beneficial for realizing efficient pressing on the thermally instable spiro-MeOTAD, UV-vis absorp-
carrier tunnelling and thereby enhanced ohmic contact29. The tem- tion spectroscopy and X-ray diffraction were employed; as the
perature of hot pressing is set at 130 °C, which is a conventional time for hot pressing exceeds 120 seconds, the featured peak of
value for EVA-based materials30,31. In addition, the pressure and spiro-MeOTAD at ~375 nm in UV-vis absorption spectroscopy

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Nature Energy Articles
a b
1 × 10–3
1.6 × 109 85 °C, 85% RH, ambient air, 500 h Cu
Ag device
Cu–Ni alloy
CNG-10 device 1 × 10–4 CNG-10
1.4 × 109

1.2 × 109 1 × 10–5

Peak area

Current (A)
1.0 × 109 1 × 10–6
3 × 106
1 × 10–7
2 × 106
1 × 106 1 × 10–8
×5
0 1 × 10–9
–0.5 –0.4 –0.3 –0.2 –0.1

)2
3
O
O

3
3

H
H

H
3
H
N

C
N

O
2
N

13

C
O
H

O
3
H

Potential (V)

(O
16

C
C

9
C

3
H
2
H
10

H
C

C
C
c Ag device d CNG-10 device e Ag device f CNG-10 device
103

Rear electrode Rear electrode

Spiro-MeOTAD Spiro-MeOTAD

Perovskite Perovskite

SnO2/FTO SnO2/FTO

y
z
x
y
z
x y
z
x y
z
x 0

Fig. 3 | The stabilizing mechanism of CNG electrodes. a, GC-MS peak areas of products for the aged Ag and CNG-10 devices. RH, relative humidity. The
peak area is with arbitrary units. b, Tafel curves for the Cu, Cu–Ni and CNG-10 electrodes in NaCl solution (3.5 wt%). c,d, The spatial distribution of I− in
the aged Ag (c) and CNG (d) devices. e,f, The spatial distribution of Ag− (e) and Cu− (f) in the aged Ag and CNG devices. The measurement area in c–f is
100 μm by 100 μm. The colour bar in c–f represents the intensity of the ions with arbitrary units.

starts to decrease (Supplementary Fig. 7c). In addition, the crys- in Supplementary Fig. 9a, and the integrated current density of
tallization peaks of spiro-MeOTAD appear in X-ray diffraction 25.77 mA cm−2 shows a minimal mismatch with the short-circuit
patterns (Supplementary Fig. 7e), indicating the recrystallization current density (JSC) from the J–V scan (26.16 mA cm−2). The
of spiro-MeOTAD32–34. However, the increase in pressure from steady-state PCE is measured to be 24.28% (Supplementary
0 to 9 bar doesn’t have an obvious influence on spiro-MeOTAD Fig. 9b), which is consistent with the PCE measured by the J–V
(Supplementary Fig. 7d,f). The results of UV-vis absorption spec- curves. The detailed photovoltaic parameters of Fig. 2b are sum-
troscopy and X-ray diffraction are consistent with the change in marized in Supplementary Table 3. The inferior performance of the
the resistance of the CNG electrodes/EVA/spiro-MeOTAD/FTO. CNG-5 and CNG-15 devices can be attributed to the lower quality
The effect of the hot pressing (temperature, 130 °C; pressure, of graphene, leading to charge accumulation at the HTM–electrode
3 bar; time, 60 seconds) on the perovskite and the charge transfer interface. This effect can be verified by capacitance–voltage (C–V)
at the perovskite–spiro-MeOTAD interface were then investi- measurements via searching the characteristic peaks in capacitance
gated. As shown in Supplementary Fig. 8a,b, the perovskite films at a specific region of bias under light35. As shown in Supplementary
before and after hot pressing show a similar morphology with a Fig. 10a–d, the C–V curve of the CNG-10 device shows no obvious
microscale grain size. The X-ray diffraction patterns both show peaks, indicating the fast charge transport in the device, whereas the
a strong featured peak of α-FAPbI3 at 13.9°, and the peak at 11.8° CNG-5 device shows a peak at approximately −1.1 V and the CNG-
for the photo-inactive δ-FAPbI3 is not observed (Supplementary 15 device shows peaks at both approximately −0.3 V and approxi-
Fig. 8c), which is consistent with the results of Supplementary Fig. mately −1.1 V, indicating the charge accumulation in those devices.
4b. Supplementary Fig. 8d exhibits the time-resolved photolumi- Twenty devices of each batch were fabricated; the histogram of
nescence results of the glass/perovskite/spiro-MeOTAD before and average PCE values is shown in Supplementary Fig. 11. The CNG-10
after hot pressing, which show a similar decay with average car- devices exhibit a narrower distribution of PCE compared with the
rier lifetimes of around 7.0 ns; the fitted results are summarized in other CNG devices and thereby a higher reproducibility due to the
Supplementary Table 2. All the results demonstrate that hot press- uniform and high-quality graphene layer, as demonstrated in Fig. 1.
ing with optimized conditions will not damage the perovskite, the To show the effect of the adhesive layer on the performance of the
spiro-MeOTAD or their interface. CNG device, we also fabricate a CNG-10 device without the EVA
Figure 2a shows the cross-sectional SEM image of a CNG device; layer, which shows a comparatively low efficiency of 20.65%, prob-
the EVA is too thin to be distinguishable so that it can realize efficient ably due to the unfilled gaps at the interface (Supplementary Fig. 12).
carrier tunnelling. The current density–voltage (J–V) curves of PSCs We further fabricated a CNG device with an aperture area of
using CNG-5, CNG-10, CNG-15 and Ag electrodes (the CNG-5, 1.02 cm2. However, a much lower PCE of 15.43% was achieved
CNG-10, CNG-15 and Ag devices, respectively) under a forward (Supplementary Fig. 13a), probably due to the non-uniformity of
scan are presented in Fig. 2b. The CNG-10 device obtained a PCE hot pressing, which may cause larger gaps at the interface beyond the
of 24.34% with an aperture area of 0.09 cm2, which is comparable thickness of EVA. In this case, we slowed down the rotation speed
with that of the Ag device (best PCE = 24.65%). The correspond- of EVA from 6,000 to 5,500 and 5,000 r.p.m., and the RS of the cor-
ing incident photon–electron conversion efficiency is provided responding devices first decreases and then suddenly increases to a

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Articles Nature Energy

1.0 95%

Normalized efficiency decay 90%

0.8

0.6
Ag devices
Au devices
0.4
SG devices
CNG-10 devices
0.2
0 1,000 2,000 3,000 4,000 5,000
Time (h)

Fig. 4 | The stabilizing effect of CNG electrodes on devices. The operational stability of the encapsulated Ag, Au, SG and CNG-10 devices at the MPP
under one sun illumination (100 mW cm−2 in ambient conditions). The devices for stability tests use the stable chlorinated graphene oxide/PTAA to
replace the spiro-MeOTAD. The initial efficiencies are illustrated in Supplementary Fig. 21. The error bars denote standard deviations for five individual
devices. Data of the cut-off normalized efficiencies are presented as 30.9 ± 0.9%, 29.1 ± 1.8%, 59.3 ± 4.1% and 95.1 ± 0.9% for the Ag, Au, SG and CNG-10
devices, respectively. The individual data are provided in the Source Data file.

much higher value (Supplementary Fig. 13b), which means that the colour of the perovskite remains black, while the perovskite under
choice of 5,000 r.p.m. leads to the formation of an insulating layer Ag turns yellow (Supplementary Fig. 16f,g). To exclude the effect
too thick to allow charge tunnelling. To allow for higher EVA thick- of electrode thickness, the permeation rates of water (water vapour
ness in localized areas with larger gaps, we mitigated resistive losses transmission rate) and oxygen (oxygen transmission rate) for the
via addition of GN in EVA to boost the conductivity. The carbonyl CNG-10 electrodes are measured and decrease to 3.32% and 5.38%
group (C=O) on the branch chain of EVA can interact with GN via of the initial values for the Cu–Ni alloy after being equipped with
van der Waals forces, as confirmed by the small blueshift (~0.33 eV) the air-tight and hydrophobic graphene (Supplementary Fig. 17a,b).
of the C=O peak measured by X-ray photoelectron spectroscopy The reduced permeability meets the requirements for encapsula-
(XPS) in Supplementary Fig. 13c, which helps the formation of tion38. To study this encapsulation effect of CNG electrodes on
a conductive network of GN in the EVA matrix36. As is shown in devices, in Fig. 3a, we conducted gas chromatography–mass spec-
Supplementary Fig. 13d, the volume resistance of EVA goes through trometry (GC-MS) to compare the volatile products escaping from
a sudden drop when the mass ratio of GN reaches 1.6 wt%, and fur- the Ag and CNG-10 devices after aging tests at 85 °C and 85% rela-
ther increase to 2.4 wt% barely improves the conductivity, indicating tive humidity in air for 500 hours39. Barely any volatile products
the formation of a stable conductive network. are found for the CNG device, except for a small quantity of NH3
The J–V curves of the devices with 0.8 wt%, 1.6 wt% and 2.4 wt% and NO. By contrast, a variety of products are detected for the Ag
GN in EVA are shown in Fig. 2c (the 0.8%, 1.6% and 2.4% devices, device, including the additive 4-tert-butylpyridine from the HTM
respectively). Obviously, the PCE of the device is greatly improved and the CH3COOH hydrolysed from the passivation layer by the
to 20.76% (certified PCE, 20.86%; Supplementary Fig. 14) when intrusion of moisture. The GC-MS results demonstrate the superior
the network is constructed (1.6% device); the corresponding damp-heat stability of the CNG device.
incident photon–electron conversion efficiency is provided in To investigate the electrochemical corrosion of the CNG elec-
Supplementary Fig. 13e, showing a minimal mismatch with the trodes, Tafel curves for Cu, Cu–Ni and CNG-10 are measured
JSC from the J–V scan (<3%). In addition, no obvious hysteresis (Fig. 3b). Compared with Cu, the corrosion current is lower at the
is observed (Supplementary Fig. 13f), and the steady-state PCE is anodic section for Cu–Ni, implying a slower corrosion rate due
measured to be 20.80% (Supplementary Fig. 15), which is consis- to alloying with Ni. For the sample of CNG-10, the self-corrosion
tent with the PCE measured by the J–V curves. However, a drop potential (Ecorr) positively shifts from −0.34 V (Cu and Cu–Ni) to
in the optoelectronic performance is found for the 2.4% device, −0.29 V, representing a much higher resistance to chemical corro-
especially in the open-circuit voltage (VOC) and the fill factor. To sion, which is due to not only the blocking of water and oxygen, but
discover the reason, we measured the transient photovoltage decay also the decrease in the migration rate of ionic species that can trig-
to analyse the charge carrier dynamics in the devices (Fig. 2d). The ger oxidation and reduction40.
faster decay of transient photovoltage for the 2.4% device suggests a The effect of the CNG-10 electrode on the suppression of
shorter charge carrier lifetime than that for the 1.6% device, which migrated ions and metal atoms in the devices is further demon-
may be related to the aggregation of GN37. The distribution of GN strated. After removing the package and peeling off the electrodes
in EVA is characterized by Raman spectra (Fig. 2e,f); apparent of the devices that were aged at the MPP for 1,000 hours, XPS mea-
aggregation of GN represented by the red regions in the figure is surement revealed an I− signal inside the CNG-10 that was much
found in EVA with 2.4 wt% GN, which may bring about a higher lower than that inside the Ag (Supplementary Fig. 18a,b), a result
concentration of defects that cause extra non-radiative losses at the that preserves the morphologies of spiro-MeOTAD and perovskite,
interface. A variety of conductive additives can be chosen to boost as shown in Supplementary Fig. 18c,d. The spatial distributions
the conductivity of the copolymer. However, to guarantee the sta- of I−, Ag−, Au− and Cu− for the aged Ag, Au and CNG devices
bility of the interface, stable materials with good dispersity will be were analysed by time-of-flight secondary ion mass spectroscopy
the priority selection. (Supplementary Fig. 18e,f and Supplementary Fig. 19a). Obviously,
the I− (Fig. 3c) and Ag− (Fig. 3e) in the aged Ag device have migrated
Stabilizing mechanism of CNG electrode. To reveal the stabilizing over the whole depth of the device. Even though the migration
mechanism of CNG, we first studied its resistance to water and oxy- of I− (Supplementary Fig. 19b) and metal atoms (Supplementary
gen. As shown in Supplementary Fig. 16a–e, the contact angle with Fig. 19c) is suppressed in the aged Au device compared with the
water in air increases from 74.9° for a Ag electrode to 102° for CNG- Ag device, there are still (AuI2)− signals (Supplementary Fig. 19d)
10, which should be beneficial for repelling water. Even if water is and Au clusters (Supplementary Fig. 19a) that are detected in the
dropped on and stays on the surface of CNG-10 for 24 hours, the perovskite layer, which is detrimental to the long-term stability

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Nature Energy Articles
of the Au device41,42. On the contrary, the I− (Fig. 3d) and Cu− illumination. We anticipate that this work will open new avenues
(Fig. 3f) in the aged CNG-10 device are almost confined to their for designing electrodes to improve the stability of PSCs.
original layers.
Methods
Materials. All the chemicals were used without further purification, including
Stabilizing effect of CNG electrode on devices. Benefiting
(1) the SnO2 electron transport material: dispersing SnO2, 15% in H2O colloidal
from the effect of the CNG electrode on resisting water and dispersion (Alfa Aesar), and deionized water (Sigma-Aldrich); (2) the perovskite
oxygen and suppressing component migration, CNG devices precursor: CH(NH2)2I (98%, TCI), CH3NH3I (98%, TCI), CH3NH3Cl (98%,
show great damp-heat and operational stabilities. The CNG-10 TCI), PbI2 (99.99%, TCI), dimethylformamide (99.8%, Sigma-Aldrich), dimethyl
devices retained 97% of their initial efficiency after the aging test sulfoxide (99.9%, Sigma-Aldrich) and isopropanol (IPA, Sigma-Aldrich);
(3) the HTMs: spiro-MeOTAD (99.8%, Ningbo Borun New Material Technology),
of heating at 85 °C with ~85% relative humidity for 1,440 hours 4-tert-butylpyridine (Xi’an Polymer Light Technology), bis(trifluoromethane)
(Supplementary Fig. 20). For the operational stability test, another sulfonimide lithium salt (99.95%, Sigma-Aldrich), acetonitrile (99.8%,
control sample using Cu–Ni alloy with bifacial sprayed graphene Sigma-Aldrich), chlorobenzene (99.8%, Sigma-Aldrich), PTAA (Sigma-Aldrich),
as the electrode (the SG device) was tested. All the encapsulated toluene (99.8%, Sigma-Aldrich); (4) the electrode: Ag and Au (99.999%, Beijing
devices were measured at the MPP with continuous 1 sun illumi- Dream Material Technology), Cu foil (99.8%, Alfa Aesar, 25 μm thick), Ni target
(99.995%, Beijing ZhongNuo Advanced Material Technology), EVA (with 40%
nation; the CNG-10 devices retained 95% of their initial PCEs ethenyl acetate, Sigma-Aldrich), GN (Alfa Aesar) for adhesive, xylene (99%,
after 5,000 hours with a small deviation across five individual cells, Aladdin) and graphene for SG device (99%, Alfa Aesar). Chlorinated graphene
while the PCEs of the SG, Au and Ag devices dropped to 59%, 47% oxide is synthesized according to a previous work11.
and 31% of their initial PCEs after ~2,500, 1,750 and 1,250 hours,
respectively (Fig. 4). The initial PCEs of the devices are summa- Synthesis of EVA-based adhesives. Different amounts of GN from 0 to 6 mg
were added to 10 ml xylene and sonicated for 1 hour to form homogeneous GN
rized in a box plot (Supplementary Fig. 21). The inferior opera- dispersions. Then 0.25 g of EVA was added into the dispersions. The samples were
tional stability of the SG device compared to the CNG device placed in a drying oven at 80 °C to swell for 1 hour. The swelled sample was further
may be ascribed to the numerous pores in overlapped sprayed stirred for 10 hours to form homogeneous EVA adhesive and EVA–GN adhesive.
graphene, which decreases the effect of suppressing component
migration. The EVA layer is also incorporated in the SG devices. Fabrication of CNG and SG electrodes. For the fabrication of the CNG electrodes,
the Cu foil was first chemically polished by immersion in an ammonium persulfate
Therefore, the main reason for the enhanced operational stability etchant solution in water (0.2 M) for 3 minutes43, which doesn’t have an obvious
of CNG devices is the CNG electrode. effect on the thickness of the Cu foil. After that, the Cu foil was sonicated one by
To further decouple the effect of the EVA layer on the stability, one with detergent, deionized water, ethanol, acetone and IPA for 15 minutes each.
we coated the EVA on the perovskite and observed the degradation Ni layers with thicknesses of 100, 200 or 300 nm were then sputtered on the Cu
of the perovskite at 85% relative humidity and 85 °C using UV-vis foil using the magnetron sputtering method followed by thermal annealing under
a 100 sccm Ar/H2 reducing atmosphere at 1,000 °C for 1 hour to form uniform
absorption spectroscopy and X-ray diffraction (Supplementary Cu–Ni alloys. By employing 5, 10 and 15 sccm of CH4 diluted in 100 sccm Ar/H2
Fig. 22). The EVA has a positive effect on preventing the decom- as a carbon source at 1,000 °C for 30 minutes, both sides of the Cu–Ni alloy were
position of perovskite for the first 200 hours, whereas an obvious protected by graphene with varying numbers of layers and quality, denoted as
drop in the absorption is found after 1,000 hours, accompanied by CNG-5, CNG-10 and CNG-15, respectively. For the fabrication of the SG electrode,
20 mg graphene was dispersed into 5 ml IPA through ball-milling for 12 hours to
a much stronger featured peak of PbI2 at 12.7°. In addition, to anal-
obtain a homogeneous dispersion. Then, 150 μl dispersion was sprayed onto both
yse the possible ability of the EVA to suppress metal atom diffu- sides of a Cu–Ni alloy followed by annealing at 85 °C (ref. 44).
sion, we coated EVA on glass/80 nm Au or glass/CN-2 and detected
the surfaces by XPS (penetration depth, 2–5 nm) before and after Sample preparation for investigating the effect of hot pressing on the
the samples were heated at 85 °C for 500 hours. To ensure that the perovskite. To simulate the real conditions, we fabricated the integral device with a
structure of FTO/SnO2/perovskite/spiro-MeOTAD/EVA/CNG-10, and then peeled
signals are from the metal diffusion, we increased the concentra- off the electrode and washed off the spiro-MeOTAD with chlorobenzene to obtain
tion of the EVA dispersion from 0.025 g ml−1 to 0.250 g ml−1. As a the perovskite sample after hot pressing (temperature, 130 °C; pressure, 3 bar; time,
result, distinct peaks of the Au 4f core level and Cu 2p core level are 60 seconds). Similarly, to prepare the perovskite sample before hot pressing, we
detected for the samples of glass/80 nm Au/EVA and glass/CN-2/ fabricated the semi-device of FTO/SnO2/perovskite/spiro-MeOTAD and washed
EVA, respectively (Supplementary Fig. 23). Therefore, it is hard off the spiro-MeOTAD with chlorobenzene.
for the original EVA to prevent metal diffusion in a CNG device. Fabrication of PSCs with different electrodes. A precursor solution composed
Both results indicate the limited effect of the thin EVA layer on the of methyl isobutyl ketone and silicon dioxide nanoparticles was brought from
long-term stability of CNG devices. Shanghai Juanrou Newtech and diluted with IPA (v/v, 1:1). The diluted solution
Finally, the manufacturing costs of the CNG electrode were was spin-coated atop the glass side of FTO substrates at 3,000 r.p.m. for 30 seconds,
estimated to be US$149.992 m−2 by considering the raw materials, followed by the thermal annealing process at 120 °C for 2 hours to remove the
solvent and obtain the anti-reflection layer. The FTO substrates were etched
magnetron sputtering and CVD (Supplementary Table 4). This with zinc powder and 6 M HCl for 15 seconds to obtain patterned substrates,
cost is about one-third of that of the evaporated Au electrode. More followed by sonication with detergent, deionized water, ethanol, acetone and
importantly, the size of our sample for CVD was restricted by the IPA for 15 minutes each. Before use, the substrates were cleaned with ultraviolet
equipment in our lab, which increased the manufacturing costs. It ozone for 20 minutes to remove the organic residues. Then a thin layer of SnO2
is expected that the manufacturing costs of a CNG electrode will be was prepared by spin-coating a SnO2 dispersion (v/v, 1:8.5 in deionized water)
at 3,000 r.p.m. for 30 seconds, followed by annealing in the ambient air at 150 °C
significantly reduced after commercialization. for 30 minutes. After the 20 minute treatment by ultraviolet ozone, the substrates
were transferred to a glove box. Then 1.5 M PbI2 in dimethylformamide/dimethyl
Conclusions sulfoxide (v/v, 9:1) was spin-coated on SnO2 at 1,500 r.p.m. for 40 seconds and
We have developed a composite electrode for PSCs that ensures effi- then a solution of CH(NH2)2I/CH3NH3I/CH3NH3Cl (90:9:9 mg ml−1) in IPA
cient and stable charge collection during the long-term operation of was spin-coated on PbI2 at a spin rate of 1,500 r.p.m. for 30 seconds, followed by
thermal annealing at 150 °C for 15 minutes in the ambient air (~30% humidity).
the devices. A Cu–Ni alloy is used as the substrate to simply tune The substrates were then transferred to the nitrogen glove box and a potassium
the WF, and strong barriers of graphene are in situ grown on both acetate (KAc) solution in IPA (1.5 mg ml−1) was spin-coated atop the perovskite at
sides. A modified adhesive layer is also introduced at the interface a spin rate of 5,000 r.p.m. for 30 seconds45. After that, the layer of spiro-MeOTAD
of the semi-device and the CNG electrode to improve the ohmic or PTAA was spin-coated on the perovskite film at a spin rate of 3,000 r.p.m. for
30 seconds. This is a dynamical spin-coating; the dissolution of the KAc might
contact. The corresponding devices retained 97% of their initial
occur if we load the HTM solution for a while and then start the rotation in static
efficiencies after 1,440 hours of a damp-heat test at 85 °C with a rela- spin-coating, leading to an inhomogeneous morphology (Supplementary Fig. 24).
tive humidity of 85%, and retained 95% of their initial efficiencies The spiro-MeOTAD was dissolved in chlorobenzene (72.3 mg ml−1) with additives
after 5,000 hours of tracking at the MPP under continuous 1 sun of 17.5 µl bis(trifluoromethane)sulfonimide lithium salt/acetonitrile (520 mg ml−1)

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Acknowledgements Additional information

We thank Z. Bao and Y. Han from the Instrumental Analysis Center of Shanghai Jiao Supplementary information The online version contains supplementary material
Tong University (China) for assistance with SEM measurements; J. Ding from the available at https://doi.org/10.1038/s41560-022-01038-1.
Instrumental Analysis Center of Shanghai Jiao Tong University (China) for assistance with
time-of-flight secondary ion mass spectroscopy measurements; X. Ding and Correspondence and requests for materials should be addressed to Yanbo Wang
N. Zhang from the Instrumental Analysis Center of Shanghai Jiao Tong University or Liyuan Han.
(China) for assistance with XPS and ultraviolet photoelectron spectroscopy Peer review information Nature Energy thanks Jin-Wook Lee and the other, anonymous,
measurements; R. Wang from the Instrumental Analysis Center of Shanghai Jiao Tong reviewer(s) for their contribution to the peer review of this work.
University (China) and K. Jiang from the Engineering Research Center for Nanophotonics Reprints and permissions information is available at www.nature.com/reprints.
and Advanced Instrument, Ministry of Education, School of Physics and Electronic
Science, East China Normal University (China) for assistance with Raman spectra Publisher’s note Springer Nature remains neutral with regard to jurisdictional claims in
measurements; X. Liu and Y. Liu from the Instrumental Analysis Center of Shanghai published maps and institutional affiliations.
Jiao Tong University (China) for assistance with GC-MS measurements; and Y. Liu and © The Author(s), under exclusive licence to Springer Nature Limited 2022

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