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Page 1 of 33 Journal of Materials Chemistry A
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DOI: 10.1039/C5TA04695E
Efficient and Low-Temperature Processed Perovskite Solar Cells Based on a Cross-linkable
Journal of Materials Chemistry A Accepted Manuscript

Hybrid Interlayer
Qin Hua,b,1, Yi Liua,1, Yu Lia, Lei Yingc, Tanghao Liua, Fei Huangc,*, Shufeng Wanga, Wei Huangd,
Published on 04 August 2015. Downloaded by Georgetown University Library on 05/08/2015 14:49:19.
Rui Zhua,b,*, Qihuang Gonga,b

a
State Key Laboratory for Artificial Microstructure and Mesoscopic Physics, School of Physics,
Peking University, Beijing, 100871, China.

b
Collaborative Innovation Center of Quantum Matter, Beijing, 100871, China.
c
Institute of Polymer Optoelectronic Materials and Devices, State Key Laboratory of
Luminescent Materials and Devices, South China University of Technology, Guangzhou,
510640, China.
d
Institute of Advanced Materials, Nanjing Tech University, Nanjing, 211816, China.
*
Corresponding authors.
1
These authors contributed equally.
Corresponding authors:
Tel.: +86 010 62750853 (Rui Zhu). Fax: +86 010 62756567 (Rui Zhu)
E-mail address: iamzhurui@pku.edu.cn (Rui Zhu); msfhuang@scut.edu.cn (Fei Huang)
1
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Keywords

Highly efficient; Low-temperature; Perovskite solar cells; Cross-linkable interlayer; Interface
engineering
Abstract
A cross-linkable conjugated polymer, poly[9,9-bis(6′-(N,N-diethylamino)propyl)-fluorene-
alt-9,9-bis-(3-ethyl(oxetane-3-ethyloxy)-hexyl)-fluorene (PFN-OX), was investigated as the n-
type interface layer for highly efficient and low-temperature processed planar heterojunction
perovskite solar cells. Hybrid composite films consisting of PFN-OX and ZnO nanoparticles
were utilized as the electron selective layers, and a remarkable power conversion efficiency over
16% was achieved. The cross-linkable PFN-OX provided a robust hybrid composite electron
selective layer, which is solvent-resistant during the device fabrication process and results in
efficient electron extraction and hole-blocking. Meanwhile, the time-resolved photoluminescence
quenching measurements indicated that the charge separation and collection processes were
improved for the devices based on PFN-OX:ZnO, in comparison with the devices using pure
PFN-OX or ZnO. Device stability and the hysteresis effect were also discussed. Moreover, this
study introduces the cross-linking concept in the perovskite solar cells, which will potentially be
an effective strategy for high performance perovskite solar cells.
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1. Introduction

Highly efficient and cost effective photovoltaic technologies are attracting increasing
attentions from both academic and industrial fields. Some candidates, such as dye-sensitized
solar cells (DSSCs),1 organic solar cells,2,3 inorganic thin film solar cells4 have been
extensively studied over the past decade. During the recent five years, a novel photovoltaic
technology, perovskite solar cells (PSSCs), has emerged as a top contender for the high
performance and low-cost photovoltaic devices.5,6,7,8,9,10,11 Compared with other candidates,
PSSCs have shown its great potential and superiority due to the inexpensive perovskite
material, the simple fabrication methods and the sky-rocketing power conversion efficiency
(PCE) from 3.8% to around 20% within only 5 years.8 Most recently, a certified PCE for
PSSCs was reported up to 20.1% with the great efforts from the Korea Research Institute of
Chemical Technology (KRICT).12
The advances of PSSCs are originally attributed to the organometal halide perovskite
photovoltaic materials, which consist of organic and inorganic hybrid components and
possess the perovskite-type crystalline structure. Due to their unique electronic and optical
properties,13,14 these hybrid organometal halide perovskites have been intensively studied in
thin-film transistors,15 light-emitting diodes16 and other photoelectric devices17 during the
past decades. The application of organometal halide perovskites in photovoltaic device
initially evolved from the DSSC technology. In 2009, hybrid perovskites were firstly used as
solar light absorber in liquid-electrolyte based DSSCs, resulting in a modest PCE of 3.8%.18
Further enhancement was later achieved by introducing the perovskite light absorber to the
mesoporous solid-state DSSCs, leading to PCEs of ~10% in 2012.19,20 Researches also
indicated that the hybrid perovskites possess the optimal bandgap, high absorption
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coefficient, small exciton binding energy, high mobilities of carriers and long exciton

diffusion length.6,21,22,23 These advances have ensured the superior photovoltaic performance
for the hybrid perovskites solar cells.

In addition to the mesoporous PSSCs, the planar heterojuncton PSSCs 24 have also been
developed, which have the advantage of low-temperature process and is suitable for the
flexible substrates.25,26 The planar heterojunction PSSC devices possess the layered
architecture, which consists of multiple functional films sandwiched between anode and
cathode. These functional films include the electron selective contacts (ESCs), perovskite
absorber layer, and hole selective contacts (HSCs).27 In order to achieve high device
performance, various approaches have been conducted. For example, morphology control of
the perovskite film28,29 and the optimization of hole-conducting materials30,31 have been
extensively studied to optimize the device performance. Moreover, intensive efforts have
also been made for interface engineering at the electron selective contacts. This provides an
effective strategy to enhance the electron collection, leading to the improved device
performance. The most commonly used ESC for planar heterojunction PSSCs is based on
the titanium oxide (TiOx) materials.32,33 Several other attempts, include the TiO2/graphene
nanocomposites,34 ZnO nanoparticles35 and the ultrathin graphene quantum dots36 were
reported as the low-temperature processed ESCs and considerable device efficiencies of
over 15% were achieved. Moreover, the surface modification strategy has also been
demonstrated to achieve the n-type contact between the active layer and the electrode.37,38,39
By modifying the surface energy of ITO substrate with Cs2CO3, a device efficiency
exceeding 15% was achieved.37 Most recently, a hybrid n-type contact consisting of doped
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TiO2 and polyelectrolyte was introduced into PSSCs and a high PCE approaching 20% was

achieved.40
In this study, a hybrid n-type interface modification based on a cross-linkable

conjugated polymer (CPs) is demonstrated in perovskite solar cells. CPs have been reported
as effective n-type interface layer in organic electronic devices and perovskite solar
cells.25,26 It is believed that the CPs layer could form dipoles at the organic/metal interface
and facilitate efficient electron transport.41,42 For example, the amino-functionalized
polyfluorene, Poly[9,9-bis(6′-(N,N-diethylamino)propyl)-fluorene] (PFN, Figure 1a), has
been used in organic light emitting devices (OLED)43 and polymer solar cells (PSCs).44
Impressive results were often achieved with the contribution of PFN-based interface.
However, considering their solubility in polar solvents, the CPs may not be compatible in
the regular PSSCs. For example, perovskite materials are often deposited onto the n-type
interface layer from its solution in the polar solvents, such as N,N-dimethylformamide
(DMF) or dimethylsulphoxide (DMSO). These solvents could re-dissolve the PFN layer.
The deposition of hole-conducting layer also involves organic halogenated solvents, which
may damage the PFN interface layer. Thus, cross-linkable conjugated polymer (PFN-OX,
Figure 1a), which shows better solvent resistance, has been chosen to form a hybrid n-type
interface layer with metal nanoparticles. With this hybrid composite as the electron-selective
layer, a remarble efficiency above 16% could be achieved.
2. Results and discussion
Comparison between PFN and PFN-OX
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Conjugated polymers (CPs) have been widely used to improve the interface contact in

organic photovoltaics (OPVs) and OLEDs. A typical example is the alcohol/water soluble
polyfluorene derivative, PFN, which contains alkylamine groups in the side chain (Figure
1a). It was reported that the work function of indium-tin-oxide (ITO) could be modified by
the amino groups in the PFN, which greatly enhanced the electron extraction in OPVs and
electron injection in OLEDs.41 Recently, PFN was also utlized in the inverted planar
heterojunction perovskite solar cells to form efficient ohmic contact between electrode and
active layer45,46 However, PFN has unfavorable solvent resistance to some polar solvents or
organic halogenated solvents, such as DMF and CB, which is undesirable during the device
fabrication of regular planar heterojunction PSSCs. On the contrary, PFN-OX, as shown in
Figure 1a, could be insoluble after being thermally cross-linked, giving a robust CP layer.
Meanwhile, as the oxetane groups are chemically bonded on the end of the side chains, the
band structure and the energy level of PFN-OX main chain could not be changed after being
cross-linked.47
The solvent resistance capability of PFN and cross-linked PFN-OX was compared
based on UV-Vis absorption shown in Figure 1b. Both the PFN and PFN-OX films were
washed by pure chlorobenzene (CB), which is the typical solvent for hole-conducting
materials in PSSCs. Besides, CB can wash out PFN more easily comparing with other polar
solvents. Thickness variation of the washed films could be monitored basing on the UV-Vis
absorption intensity. As shown in Figure 1b, before solvent washing, PFN-OX film has
similar absorption intensity as that of PFN. After being washed by CB, the absorption
intensity of PFN decreased by ~70%, indicating the loss of ~70% PFN. In contrast, no
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obvious absorption changes were observed for the cross-linked PFN-OX film after CB

washing. This result confirms the robustness of the cross-linked PFN-OX.
PFN and PFN-OX was then incorporated into regular planar heterojunction perovskite
solar cells with the structure of ITO/ESCs/CH3NH3PbI3/Spiro-OMeTAD/Au (as shown in
Figure 2a). In addition, ZnO nanoparticles were also utilized together with the conjugated
polymers to form the hybrid electron-selective layer in this study. The deposition of
CH3NH3PbI3 films on different ESCs followed the regular two-step sequential-deposition
method.11 However, it should be mentioned that no annealing process was performed after
the deposition of CH3NH3PbI3 film. This will avoid the possible reactions between the
perovskite layer and ZnO materials.37
Table 1 summarizes the device performances with different ESCs measured under
simulated AM 1.5G 100 mW·cm-2 illumination. The mean values and standard deviations of
the characterization parameters are from 7 to 15 solar cells for different type of devices. For
the typical device with pristine ITO, poor performance was obtained. The device
performance became better as long as the ESCs were inserted. The power conversion
efficiency (PCE) of the device with pure PFN-OX was 11.1%, while only 10.2% for pure
PFN. For the device using pure sol-gel-processed ZnO nanoparticles as ESC, a PCE of 13.7%
was achieved. For the device using the PFN:ZnO hybrid electron selective composites, a
PCE of 12.8% was attained, which was a little lower than that based on pristine ZnO. By
contrast, the device based on PFN-OX:ZnO composite exhibited a remarkable PCE of
15.5%, with an open-circuit voltage (Voc) of 1.02 V, short-circuit current density (Jsc) of 20.2
mA·cm-2 and fill factor (FF) of 0.75. The high PCE is mainly ascribed to the improved FF
in the PFN-OX:ZnO-based device, which is often influenced by the series resistance (Rs)
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and the shunt resistance (Rsh).45,46 Compared with the device based on PFN-OX, the device

with PFN-OX:ZnO showed decreased Rs from 6.9 Ω·cm2 to 4.0 Ω·cm2 and increased Rsh
from 1909.6 Ω·cm2 to 3355.4 Ω·cm2, resulting in the improved FF from 0.68 to 0.75. These
results suggested that a favourable ohmic contact between electrode and perovskites could
be achieved with the hybrid ESCs. In summary, the device based on the PFN-OX:ZnO
hybrid n-type contacts attained the best photovoltaic performance.
Device Optimization
According to previous reports,47,48 thickness of CP layer is critical to the device
performance. On one hand, the CP layer should have enough thickness to ensure the
effective electron selection and transportation.48 On the other hand, the relatively thicker CP
layer could introduce larger series resistance48 and result in a lower FF. In order to explore
the optimum thickness conditions for the hybrid n-type contact, the thickness of PFN-OX and
ZnO in the hybrid composite was optimized. PFN-OX solutions with varied concentrations
from 0.25 mg·mL-1 to 2.0 mg·mL-1 were spin-coated on ITO substrates for the device
fabrication. Figure 2c exhibits the representative device performance. (The mean values and
standard deviations are showed in Table S1). With increased thickness of PFN-OX, the Voc
shows little change, while the Jsc and FF could reach the best at the concentration of 0.5
mg·mL-1. A Voc of 1.02 V, Jsc of 21.1 mA·cm-2 and FF of 0.70 were achieved with this
optimized PFN-OX thickness, resulting in the PCE of 15.1%. For the optimization of ZnO
layer in the hybrid composite, results indicated that one layer of ZnO nanoparticles (10 ~
13nm) on the PFN-OX layer showed the best performance. Further coatings of ZnO
nanoparticles did not give better device performance, although the ZnO film could be more
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compact. In order to ensure the reproducibility of the device fabrication, 50 devices were

prepared based on PFN-OX:ZnO. The statistics of device performance characteristics is
shown in Figure S1. The champion PCE of 16.2% was achieved, with a Voc of 1.03 V, Jsc of
20.7 mA·cm-2, and FF of 0.76, as shown in Figure 2d. Incident photon-to-current
conversion efficiency (IPCE) spectrum was also obtained for this device (inset of Figure 2d).
The Jsc calculated from IPCE spectrum is 18.9 mA·cm-2, which agrees with the Jsc measured
from J-V characterization under standard AM1.5G illumination.
Understanding the hybrid n-type contacts
Interface engineering between electrode and light-harvesting perovskite layer is
important to achieve high device performance. The introduction of proper interfacial
materials, the optimization of interface barrier and the formation of ohmic contact with
minimum resistance and high charge selectivity should be considered to realize an ideal
interface.49,50 Recent progresses also demonstrated the importance of interface engineering
in the PSSCs with the mesoscopic structure51 or the planar heterojunction structure.40
According to the above device optimization, interface engineering based on PFN-OX:ZnO
hybrid n-type contact could provide the best performance for PSSCs. To understand the
advances of this hybrid composite contact, surface work function analysis, surface
morphology characterization and interface interaction were investigated.
Firstly, it is well known that the amino groups in the functional polyfluorene could
generate interface dipoles and lower the work function of ITO. The dipoles at the interface
could increase the built-in potential and result in a higher Voc.44 This was approved in the
devices based on PFN or PFN-OX in comparison to the device based on pristine ITO (table
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1). For PFN-OX, UPS results (Figure 3a) indicated that the surface work function of ITO

was 0.9 eV closer to vacuum level after PFN-OX modification. This is consistent with
previous reports.48 The work function of PFN-OX:ZnO was 4.2 eV, which was almost the
same as that of pure ZnO. Figure 3b shows the energy level diagram of the device based on
UPS analysis. The work function of ITO was 4.4 eV. The hybrid composite film of PFN-
OX:ZnO exhibited the work function of 4.2 eV, while the conduction band minimum
(CBM) of CH3NH3PbI3 was reported as 3.9 eV.19 It is obvious that the favourable energy
level alignment could be achieved between PFN-OX:ZnO and CH3NH3PbI3. This will lead
to the efficient carrier extraction and transportation without excessive interface
recombination or quasi-Fermi level splitting in light-harvesting CH3NH3PbI3 layer.40
In addition to the matched surface work functions, the formation of ohmic contact
with minimum resistance should also be considered for an ideal interface.49 As
aforementioned, the device based on hybrid PFN-OX:ZnO interface showed an increased
Rsh and deceased Rs, indicating that the hybrid PFN-OX:ZnO contacts could provide an
effective ohmic contact and facilitate the electron extraction from the perovskite absorber
to ITO. Comparing the devices based on PFN:ZnO and PFN-OX:ZnO, the device
performance in table 1 indicated that PFN-OX:ZnO composite film may form a better
ohmic contact at the interface than PFN:ZnO. This could be understood based on the
morphology analysis. Figure 7 shows some top-view SEM images. In Figure 7a, a few pin-
holes can be observed in the perovskite film formed on PFN-OX:ZnO film; meanwhile, the
SEM of PFN:ZnO hybrid layer (Figure 7b) also indicates that ZnO nanoparticles did not
form a compact film. These pin-holes could provide the penetration channel for the DMF
in perovskite solution and CB in Spiro-OMeTAD solution. Thus, the PFN:ZnO or PFN-
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OX:ZnO layer could be corroded by DMF and CB solvents if the layer was not robust

enough. Compared with PFN, PFN-OX could be thermally cross-linked, resulting in robust
polymer networks. This will prevent the polar solvents from damaging the PFN-OX:ZnO
hybrid interface layer. As a result, the PFN-OX:ZnO could provide a better and robust
interface contact, leading to a higher PCE.
The interfacial interaction was further investigated by the time-resolved
photoluminescence (TRPL) quenching study. TRPL quenching has been successfully used
to determine excitons’ life time, diffusion rate and diffusion length.22,23,52 It is also helpful
to explore the exciton quenching at the interface between ESCs and perovskite light
absorbing layer. In this work, TRPL quenching was performed to compare the different
ESCs including PFN-OX, ZnO and hybrid PFN-OX:ZnO. The thickness of CH3NH3PbI3
film was about 330 nm. The samples were excited at 517 nm by a two-stage optical
parametric amplifier, and the TRPL decays were acquired at the peak emission wavelength
of 770 nm. The observed PL decays were fitted with two exponential decay curves to yield
the lifetime of excitons or carriers according to the one-dimensional diffusion model (the
longer life time was used).22,23 Figure 4 shows the TRPL quenching results. The PL decay
of the neat CH3NH3PbI3 film on glass substrate exhibited a lifetime of 8.9 ns, which was
consistent with the reported results.22,23 When the CH3NH3PbI3 film formed a contact with
PFN-OX or ZnO, the carrier lifetime both reduced to 5.7 ns, respectively. This indicates
that PFN-OX and ZnO could provide the similar charge-carrier transfer process at the
interface. Moreover, the lifetime of CH3NH3PbI3 further dropped to 4.6 ns for the hybrid
PFN-OX:ZnO contacts. The shorter life time based on PFN-OX:ZnO reveals that PFN-
OX:ZnO provided the faster charge transfer from perovskite to ITO in comparison to pure
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PFN-OX or ZnO. In other words, the charge separation and collection process could be

more efficient based on the hybrid PFN-OX:ZnO contacts. This may also be ascribed to the
appropriate energy levels alignment between PFN-OX:ZnO and CH3NH3PbI3 without

excessive interface recombination, as well as the ohmic contact to facilitate the electron
extraction from the perovskite absorber to ITO. These PL quenching results were in
consistent with the device performance listed in table1.
Based on the above characterization and discussions, the advances of the hybrid PFN-
OX:ZnO contacts can be summarized with its superior electrical and chemical properties.
These include the appropriate energy levels alignment, the ohmic contact, and the efficient
electron extraction.
The hysteresis effect
Recently, researchers are paying more and more attentions on the hysteresis effect of
perovskite solar cells, which manifests the differences in current-voltage (I-V) curves
performed in different scanning direction in current-voltage measurement.53 The hysteresis
effect is a common phenomenon observed in thin film solar cells, such as CdTe, GIGS and
amorphous silicon.54,55,56 Hysteresis effect typically originated from the capacitive character
of devices. Several dynamic models based on diode and capacitances have been built to
understand the inside mechanism.56,57 In fact, none of the reported models could be
universally verified to elaborate the hysteresis effect in all types of solar cells.56 The
existence of defects states, ion migration and deep trapping of the charger carrier
accumulation have also been proposed to understand the hysteresis effect in thin film solar
cells.58,59
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In PSSCs, the hysteresis effect has been detected both in the mesoscopic and the planar

heterojunction device structures.40,53 Those conclusions obtained in thin film solar cells have
been speculated for the hysteretic behaviour in PSCCs.60 However, the hysteresis effect in
PSSCs seems to be more complicated due to the organic-inorganic hybrid crystal structure
of the perovskites. In addition to the existence of defects states, ion migration and deep
trapping of the charger carrier accumulation discussed in thin film solar cells, several other
mechanisms have also been proposed. For example, the ferroelectricity,61 the polarization
effects originating from the lattice distortion and the orientation of MA+-dipoles,60,62 the
changes of the contact conductivity63 and the significant halide ion mobility64 have been
studied to understand the hysteresis effect in perovskite solar cells. To date, the exact
conclusions for the origin of hysteresis effect haven’t been established yet, although the
hysteresis could be almost eliminated through tuning the material morphology, optimizing
the interface in mesoscopic structure, or utilizing the inverted device architectures.65,66,67.
For the regular planar heterojunction PSSCs, so far, there wasn’t any convincing
example showing the complete elimination of hysteresis. According to some recent reports,
the n-type interface engineering seems not to provide an effective solution for hysteresis
effect.32,37,40 In the present efforts, the hysteresis effect was also observed for the device
based on hybrid PFN-OX:ZnO n-type contact. Figure 5 shows the hysteresis
characterization in a representative PFN-OX:ZnO-based device measured on reverse scan
(from forward bias to short circuit) or forward scan ( from short circuit to forward bias). For
reverse scan, the Jsc, Voc, and FF values are 20.7 mA·cm-2, 1.00 V, and 0.69, respectively,
yielding a PCE of 14.3%. For the forward scan the characterizations were 20.9 mA·cm-2,
0.90 V, and 0.54, with a PCE of 10.2%.
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Stability test
Preliminary long-term stability investigation for the perovskite solar cells based on
PFN-OX:ZnO was carried out under ambient conditions (Temperature ~20 °C, humidity
~10%). Figure 6 shows the stability results for the unencapsulated devices stored in air for
600 h. During the initial 100 h after the device fabrication, the Voc was very stable, and the
Jsc decreased while the FF increased, resulting in little change in PCE. Then, the PCE
showed clear decrease after stored for 240 h and this was ascribed to the simultaneous
decreased in Jsc and Voc. For the next 300 h, the efficiency decreased slowly. Compared
with the initial performance, the device showed ~15% decrease in PCE after being stored
in the ambient condition without encapsulation for 600 h.
The hybrid PFN-OX:ZnO based perovskite solar cells have the similar thermal
stability with the ZnO-based devices. The thermal instability of ZnO-based perovskite
solar cells have been reported by both our previous work37 and other researches68. Figure
7c-f show the decompose process of CH3NH3PbI3 depositing on ZnO interface. After
heating at 100 °C for 1 h, the dark brown CH3NH3PbI3 film transforms to a bright yellow
film. Besides, the morphologies of the yellow-coloured byproducts (Figure 7g) are very
different from the yellow PbI2 precursor (figure 7e). The annealed ITO/ZnO/CH3NH3PbI3
substrate was subsequently washed by DMF. Figure 7h reveals that the pristine ZnO
nanoparticles were washed off, indicating the possible Lewis acid-base chemical reaction
between the perovskite and ZnO nanoparticles at high temperature. The proposed
mechanism for the perovskite bleaching is illustrated in Figure S2. CH3NH3PbI3 may
firstly degrade to volatile CH3NH2, inorganic PbI2 and (ionic salt) HI following the
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reaction Figure S2a.69 The acid-base chemical reaction between ZnO and HI (strong acid)

or CH3NH3I could easily produce H2O,62, 68 which is believed to be one of the most critical
reasons for CH3NH3PbI3 decomposition. The possible degrading pathways of perovskites

by the presence of water and ZnO have been showed in Figure S2c basing on the reported
literature.62
3. Conclusions
In summary, the highly efficient and low-temperature processed planar heterojunction
perovskite solar cells based on the cross-linked conjugated polymer, PFN-OX, were
demonstrated. The cross-linked PFN-OX could provide a robust electron selective layer
which possesses the superiority in electron extraction and hole-blocking. Hybrid composite
film consisting of PFN-OX and ZnO nanoparticles were utilized as the electron selective
layer, and a remarkable power conversion efficiency over 16% was achieved. The hybrid
composite of PFN-OX:ZnO could not only achieve the appropriate energy level alignment
between the perovskite material and ITO electrode, but also form optimized ohmic contact
with minimum resistance and high charge selectivity. Moreover, the charge separation and
collection processes were improved for the devices based on PFN-OX:ZnO in comparison
with the devices using pure PFN-OX or ZnO from the TRPL results. This study introduces
the cross-linking concept in the perovskite solar cells, which will potentially be an effective
strategy to achieve the high performance perovskite solar cells.
Experimental section
Materials: CH3NH3I was synthesized from CH3NH2 and HI based on the literature procedures.
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37
ZnO nanoparticles were synthesized from the zinc acetate dehydrate and potassium hydroxide

according to the reported literature.35 PFN was prepared according to the published procedure68
and PFN-OX was synthesized according to polymerization reactions carried out by palladium(0)-
catalyzed Suzuki cross-coupling reactions as the reported methods.47 The molecular weight (Mn)
of PFN and PFN-OX were 25.1 kDa and 29.5 kDa, respectively. The polydispersity (PDI) of
PFN and PFN-OX were 2.8 and 2.9. The Mn and PDI were estimated by gel permeation
chromatography (GPC) with Tetrahydrofuran (THF) as the eluent and linear polystyrene as the
standard. Besides, all liquid reagents, such as DMF, 2-propanol (IPA) and chlorobenzene (CB),
were purchased from commercial sources (Acros) and used as received. PbI2 was purchased from
Sigma Aldrich, and Sipro-OMeTAD from SunaTech.
Devices fabrication: The devices were fabricated on pre-patterned ITO glass substrates that
were cleaned with diluted detergent, deionized water, acetone, and IPA successively. Then, PFN-
OX or PFN in a solution of methanol: acetic acid (100: 1 v/v) was spin-coated (2000 rpm for 25
s) onto the substrates. The PFN-OX was cross-linked after heating the substrates at 120 °C under
fluorescence lamp illumination (no UV lamps required) for 20 min in air. The concentration of
PFN was 0.5 mg·mL-1. The concentration of PFN-OX varied according to different requirements.
After that, the ZnO layer was formed by spin-coating at 2500 rpm for 20 s and heated at 120 °C
for 3 min. All the procedures above were prepared in ambient environment of temperature
~20 °C and humidity ~20%. The solution of PbI2 in DMF with a concentration of 461 mg·mL-1
was spin-coated at 2500 rpm for 15 s and dried at 75 °C for 10 min in a N2 glovebox. The
samples were then dipped in a CH3NH3I solution (10 mg·mL-1 in 2-propanol) for 30 s without
further annealing. The Spiro-OMeTAD-based hole-transporting layer (80 mg of Spiro-OMeTAD,
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17.5 μL of lithium bis (trifluoromethanesulfonyl)-imide (Li-TFSI) solution (520 mg of Li-TFSI

in 1 mL of acetonitrile) and 28.5 μL of 4-tert-butylpyridine all dissolved in 1 mL of CB) was
subsequently deposited onto the prepared substrate at 2000 rpm for 30 s in the N2 glovebox.
Finally, gold electrode (80 nm) was deposited as the back contact through thermal evaporation.
Device characterization: The devices (active area: 0.09 cm2) were illuminated under 100
mW·cm-2 by a 150 W Class AAA solar simulator (XES-40S1, SAN-EI) with an AM 1.5G filter.
Light intensity of 100 mW·cm-2 was determined by a standard monocrystal silicon photodiode
calibrated by the Newport TAC-PV lab. The current–voltage curves were measured using a
Keithley 2400 source-measure unit. The IPCE spectra were measured in air using a lock-in
amplifier coupled with a monochromator (Crowntech, Qtest Station 2000).37 The light intensity
from the monochromator was calibrated by using a standard single-crystal Si photovoltaic cell.
All the measurements were performed in ambient conditions at room temperature on the devices
without encapsulation (temperature ~20 °C, humidity ~20%).
The ultraviolet-visible (UV-Vis) spectrum was recorded with the Agilent 8453
spectrophotometer. Ultraviolet photoelectron spectroscopy (UPS) was observed with
Imaging Photoelectron Spectrometer (Axis Ultra, Kratos Analytical Ltd.). Scanning electron
microscopy (SEM) images were collected by an FEI Nova_NanoSEM 430 field-emission
SEM. The time-resolved photoluminescence (TRPL) decay spectra were recorded using a
streak camera system (HAMAMATSU C10910) with 1ps temporal resolution. All the
samples were excited at 517 nm by a two-stage optical parametric amplifier (OperA Solo,
Coherent) configured with an amplified Ti: Sapphire laser system (Legend, Coherent) with a
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repetition rate of 1 KHz and a pulse duration of 35 fs. All the photoluminescence spectra

were measured under ambient conditions.
Acknowledgments
This work was financially supported by the National Natural Science Foundation of China
(61377025, 91433203, and 11121091) and the 973 Program of China (2015CB932203). The
authors thank Prof. Xinqiang Wang for the calibration of solar simulator, Prof. Lixin Xiao for
IPCE measurement. R. Z. is grateful to Prof. Yang Yang at UCLA for providing the guide of
solar energy research.
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Figures and Captions

Figure 1. (a) Chemical structures of PFN and PFN-OX. (b) UV-Vis absorption spectra of PFN
film and the cross-linked PFN-OX film before and after being washed by pure chlorobenzene.
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Figure 2. (a) Device architecture. (b) Scanning electron microscopy (SEM) cross-sectional
image of a perovskite solar cell based on PFN-OX:ZnO. (c) Photovoltaic performance
characterization for the devices based on PFN-OX:ZnO with varied PFN-OX coating
conditions. Insert: Summary of the device performance measured under AM 1.5G 100
mW·cm-2 illumination. (d) The best performance achieved for the perovskite solar cells
based on the hybrid PFN-OX:ZnO contact. Inset: the IPCE spectrum for the best device.
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Figure 3. (a) The UPS secondary cutoff of the pristine ITO, ITO/PFN-OX:ZnO, ITO/PFN-
OX, ITO/ZnO. (b) The schematic energy level diagram.
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Figure 4. Time-resolved photoluminescence measurements for the perovskites with
different electron selective contacts.
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Figure 5. The current density-voltage curves for a representative cell measured in standard
AM 1.5G 100 mW·cm-2 illumination by forward scan and reverse scan.
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Figure 6. The stability test of the perovskite solar cell based on PFN-OX:ZnO.
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Figure 7. Surface SEM images for ITO/PFN-OX:ZnO/CH3NH3PbI3 (a) and ITO/PFN-
OX:ZnO (b). The stability test of the perovskite solar cell based on ZnO nanoparticles: the
surface scanning electron microscopy (SEM) images of pristine ITO (c), ITO/ZnO (d),
ITO/ZnO/PbI2 (e), ITO/ZnO/CH3NH3PbI3 (f), ITO/ZnO/CH3NH3PbI3, after heating at
100 °C for 1 h (g), ITO/ZnO/CH3NH3PbI3, after heating at 100 °C for 1 h and washed by
N,N-dimethylformamide (DMF) in glovebox (h). Insert: the substrate samples in the devices
fabrication process.
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Table 1. Summary of the typical device performance with different ESCs under AM1.5G 100

mW·cm-2 illumination. The mean values and standard deviations of the characterization
parameters are from 7 to 15 solar cells basing on different ESCs.

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Table of Contents:

Highly efficient and low-temperature processed planar heterojunction perovskite solar cells
based on hybrid PFN-OX:ZnO electron-selective layer, were demonstrated.

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Efficient and Low-Temperature Processed Perovskite Solar Cells Based on a Cross-linkable

Journal of Materials Chemistry A Accepted Manuscript

Rui Zhua,b,*, Qihuang Gonga,b

Peking University, Beijing, 100871, China.

Luminescent Materials and Devices, South China University of Technology, Guangzhou,

E-mail address: iamzhurui@pku.edu.cn (Rui Zhu); msfhuang@scut.edu.cn (Fei Huang)

Journal of Materials Chemistry A Accepted Manuscript

A cross-linkable conjugated polymer, poly[9,9-bis(6′-(N,N-diethylamino)propyl)-fluorene-

alt-9,9-bis-(3-ethyl(oxetane-3-ethyloxy)-hexyl)-fluorene (PFN-OX), was investigated as the n-

efficient electron extraction and hole-blocking. Meanwhile, the time-resolved photoluminescence

an effective strategy for high performance perovskite solar cells.

Journal of Materials Chemistry A Accepted Manuscript

performance and low-cost photovoltaic devices.5,6,7,8,9,10,11 Compared with other candidates,

Chemical Technology (KRICT).12

past decades. The application of organometal halide perovskites in photovoltaic device

mesoporous solid-state DSSCs, leading to PCEs of ~10% in 2012.19,20 Researches also

Journal of Materials Chemistry A Accepted Manuscript

for the hybrid perovskites solar cells.

reported as the low-temperature processed ESCs and considerable device efficiencies of

Journal of Materials Chemistry A Accepted Manuscript

In this study, a hybrid n-type interface modification based on a cross-linkable

and facilitate efficient electron transport.41,42 For example, the amino-functionalized

polyfluorene, Poly[9,9-bis(6′-(N,N-diethylamino)propyl)-fluorene] (PFN, Figure 1a), has

layer, a remarble efficiency above 16% could be achieved.

2. Results and discussion

Comparison between PFN and PFN-OX

Journal of Materials Chemistry A Accepted Manuscript

fabrication of regular planar heterojunction PSSCs. On the contrary, PFN-OX, as shown in

Journal of Materials Chemistry A Accepted Manuscript

solar cells with the structure of ITO/ESCs/CH3NH3PbI3/Spiro-OMeTAD/Au (as shown in

CH3NH3PbI3 films on different ESCs followed the regular two-step sequential-deposition

perovskite layer and ZnO materials.37

contrast, the device based on PFN-OX:ZnO composite exhibited a remarkable PCE of

Journal of Materials Chemistry A Accepted Manuscript

hybrid n-type contacts attained the best photovoltaic performance.

According to previous reports,47,48 thickness of CP layer is critical to the device

Journal of Materials Chemistry A Accepted Manuscript

20.7 mA·cm-2, and FF of 0.76, as shown in Figure 2d. Incident photon-to-current

from J-V characterization under standard AM1.5G illumination.

Understanding the hybrid n-type contacts

Interface engineering between electrode and light-harvesting perovskite layer is

important to achieve high device performance. The introduction of proper interfacial

interface.49,50 Recent progresses also demonstrated the importance of interface engineering

According to the above device optimization, interface engineering based on PFN-OX:ZnO

morphology characterization and interface interaction were investigated.

Journal of Materials Chemistry A Accepted Manuscript

to the efficient carrier extraction and transportation without excessive interface

recombination or quasi-Fermi level splitting in light-harvesting CH3NH3PbI3 layer.40

with minimum resistance should also be considered for an ideal interface.49 As

aforementioned, the device based on hybrid PFN-OX:ZnO interface showed an increased

in perovskite solution and CB in Spiro-OMeTAD solution. Thus, the PFN:ZnO or PFN-

Journal of Materials Chemistry A Accepted Manuscript