Research Article

www.acsami.org

Colloidal Precursor-Induced Growth of Ultra-Even CH3NH3PbI3 for

High-Performance Paintable Carbon-Based Perovskite Solar Cells
Xiaowen Chang,† Weiping Li,† Haining Chen,*,†,‡ Liqun Zhu,† Huicong Liu,† Huifang Geng,† Sisi Xiang,†
Jiaming Liu,† Xiaoli Zheng,‡ Yinglong Yang,‡ and Shihe Yang*,‡
†
School of Materials Science and Engineering, Beihang University, No. 37 Xueyuan Road, Haidian District, Beijing 100191, People’s
Republic of China
‡
Department of Chemistry, The Hong Kong University of Science and Technology, Clear Water Bay, Kowloon, Hong Kong
*
S Supporting Information

ABSTRACT: Carbon-based hole transport material (HTM)-

free perovskite solar cells (PSCs) have attracted intense
attention due to their relatively high stability. However, their
power conversion efficiency (PCE) is still low, especially for
the simplest paintable carbon-based PSCs (C-PSCs), whose
performance is greatly limited by poor contact at the
perovskite/carbon interface. To enhance interface contact, it
is important to fabricate an even-surface perovskite layer in a
porous scaffold, which is not usually feasible due to roughness
of the crystal precursor. Herein, colloidal engineering is
applied to replace the traditional crystal precursor with a
colloidal precursor, in which a small amount of dimethyl
sulfoxide (DMSO) is added into the conventional PbI2
dimethylformamide (DMF) solution. After deposition, PbI2(DMSO) adduct colloids (which are approximately tens of
nanometers in size) are stabilized and dispersed in DMF to form a colloidal film. Compared with PbI2 and PbI2(DMSO) adduct
crystal precursors deposited from pure DMF and DMSO solvents, respectively, the PbI2(DMSO) adduct colloidal precursor is
highly mobile and flexible, allowing an ultra-even surface to be obtained in a TiO2 porous scaffold. Furthermore, this ultra-even
surface is well-maintained after chemical conversion to CH3NH3PbI3 in a CH3NH3I solution. As a result, the contact at the
CH3NH3PbI3/carbon interface is significantly enhanced, which largely boosts the fill factor and PCE of C-PSCs. Impressively, the
achieved champion PCE of 14.58% is among the highest reported for C-PSCs.
KEYWORDS: carbon-based perovskite solar cells, hole transport material-free, interface contact, dimethyl sulfoxide, dimethylformamide

■ INTRODUCTION
Organic−inorganic hybrid perovskite solar cells (PSCs) have
distinct reasons for the different structure-specific devices of C-
PSCs. The complicated device structure of the multilayer meso
attracted much attention due to their rapid increase in power C-PSCs developed by Han’s group16,17,25 makes the deposition
conversion efficiency (PCE) from 3.8% in 2009 to 22.1% in of high-quality perovskite difficult. The embedment method for
2016.1−7 However, the low stability of these devices has producing C-PSCs developed by Yang’s group19,26−28 has
strongly prohibited their practical application. This low stability simplified the structure of these devices. However, the carbon
results not only from the characteristic properties of hybrid electrode on the PbI2 layer is weak, which may induce many
organic−inorganic materials but also from unstable and air- cracks and decrease the device’s performance. The develop-
sensitive organic hole transport materials (HTMs; such as ment of paintable C-PSCs further simplified the fabrication
spiro-OMeTAD).8,9 Fortunately, researchers have proved that process and enhanced the mechanical properties of the
perovskite (e.g., CH3NH3PbI3 or MAPbI3) can serve as both a electrode, but the postdeposition of a carbon electrode on
light harvester and hole transporter. 10−15 This unique perovskite leads to poor contact at the interface.29−33 Recently,
ambipolar nature makes HTM-free PSCs possible. Promisingly, we partially solved this problem by fabricating an even-
low-cost and highly stable carbon materials have been perovskite surface to enhance the interfacial contact through
demonstrated to serve as an efficient hole extraction electrode solvent engineering (introducing cyclohexane into a MAI IPA
in HTM-free PSCs. Carbon-based HTM-free PSCs (C-PSCs) solution) during the conversion of PbI2 to MAPbI3, which
have been widely accepted as the most stable PSCs and have
the most potential to be used in commercialized devices.16−24 Received: August 8, 2016
Unsatisfactorily, the PCEs of C-PSCs still largely lag behind Accepted: October 14, 2016
those of traditional PSCs with HTMs. Additionally, there are Published: October 14, 2016

© 2016 American Chemical Society 30184 DOI: 10.1021/acsami.6b09925

ACS Appl. Mater. Interfaces 2016, 8, 30184−30192
ACS Applied Materials & Interfaces Research Article

Figure 1. Morphology of the DMF (H), DMF, DMSO, and DMF/DMSO Pb−I precursors: (a1−d1) solvent composition and optical photographs,
(a2−d2) SEM images, and (a3−d3) AFM images.

increased the PCE to over 14%.34 However, although the use of achieved for the paintable C-PSCs, a value among the highest
a mixed solvent can avoid the generation of large MAPbI3 PCE levels for C-PSCs.5,20,22,23,34,40−45
crystals, the rough morphology of the PbI2 crystal layer due to
its ease of crystallization from N,N-dimethylformamide (DMF)
still limits the evenness of MAPbI3, which suppresses the
■ RESULTS AND DISCUSSION
To prepare the colloidal Pb−I precursor, a mixed solvent
interfacial contact and photovoltaic performance of paintable containing DMF and DMSO (9:1 volume ratio) was used as
C-PSCs. the solvent for the PbI2 solution. In order to make a reasonable
As demonstrated above, preparing an even PbI2 layer is comparison, pure DMF and DMSO were also used as solvents
necessary for a more even MAPbI3. Additionally, prohibiting for the PbI2 solution. To deposit the Pb−I precursor on a TiO2
the crystallization of PbI2 crystals after deposition should be a porous scaffold, spin-coating was applied. The conventional
useful strategy to prevent the roughening of the surface. PbI2 layer was prepared by spin-coating the PbI2 DMF solution
Dimethyl sulfoxide (DMSO) could retard the crystallization of followed by heating at 100 °C for 5 min; this is termed the
PbI2, but the strong interaction between DMSO and Pb2+ DMF (H) Pb−I precursor. Additionally, a PbI2 layer prepared
would facilitate the formation of PbI2(DMSO) adduct crystals, from the PbI2 DMF solution without heating was also
which would also roughen the Pb−I precursor.7,35−39 Herein, in investigated and termed the DMF Pb−I precursor. Similarly,
order to prevent the crystallization of PbI2 and PbI2(DMSO) Pb−I precursor films prepared from PbI2 DMSO and DMF/
adducts, a mixed solvent of DMF/DMSO was applied in which DMSO solutions without heating were termed the DMSO and
DMSO could retard the crystallization of PbI2; furthermore, the DMF/DMSO Pb−I precursors, respectively.
presence of DMF could also suppress the formation of The four as-prepared Pb−I precursor layers show obviously
PbI2(DMSO) adduct crystals. It is demonstrated that a PbI2 different colors, as shown in Figure 1a1−d1, from brown yellow
DMF/DMSO solution can achieve an ultra-even Pb−I for DMF (H) Pb−I, bright yellow for DMF Pb−I, and almost
precursor containing small PbI2(DMSO) adduct colloids transparent for DMSO Pb−I. The difference in color indicates
(tens of nanometers in size). This precursor afforded MAPbI3 possible variations in their morphologies and/or compositions.
with an ultra-even surface that enhanced the interfacial contact To evaluate the differences in their morphologies, SEM (Figure
with the carbon electrode, which significantly improved the fill 1a2−d2) and AFM (Figure 1a3−d3) images were recorded. The
factor (FF) of these paintable C-PSCs. A PCE of 14.58% was conventional DMF (H) Pb−I precursor exhibits a mountain-
30185 DOI: 10.1021/acsami.6b09925
ACS Appl. Mater. Interfaces 2016, 8, 30184−30192
ACS Applied Materials & Interfaces Research Article

Figure 2. Characterization of the different Pb−I precursor films: XRD patterns (a), FT-IR spectra (b), UV−vis diffuse reflectance spectra (c), and
schematic of the formation (d) of the DMF (H), DMF, DMSO, and DMF/DMSO Pb−I precursors.

like surface, suggesting a rough surface. This morphology was the small angle region are likely related to PbI2(DMF) adducts
confirmed from the AFM image, in which the roughness factor as the DMF molecules could be easily inserted into the gaps
was measured to be about 37 nm. In addition to having a between PbI2 layers. When the Pb−I precursor was deposited
similar mountain-like surface, many small pinholes also exist on from a DMSO solvent, many other new diffraction peaks at
the DMF Pb−I precursor, which was not heat treated; this is around 9.8, 15.8, 18.6, 21.7, and 29.5° appeared, which could be
well-reflected in its AFM image, with the roughness factor indexed to the previously reported diffraction peaks of
increasing to 54 nm. Differing from the above two precursors, PbI2(DMSO) adducts.7,39 Although DMSO has been proven
the DMSO Pb−I precursor shows a completely different to effectively prevent the crystallization of PbI2 due to the
morphology with two significantly different parts. One part strong interaction between Pb2+ and DMSO molecules, this
shows an even surface but with many obvious cracks, whereas strong interaction has been widely observed to form
the other part shows many vivid grain-like embossments, PbI2(DMSO) adducts, in which DMSO molecules are inserted
partially suggesting strong crystallinity. These two different into the gaps between the PbI2 layers.7,39,46 Our present result
regions could also be well-observed from the AFM images, with indicates that PbI2(DMSO) adducts crystallize easily, which
a low roughness factor (14 nm) (Figure S2) for the even part induces the formation of a rough surface morphology for the
and a considerably higher roughness factor (107 nm) for the DMSO Pb−I precursor. The FT-IR spectra also confirmed the
strong crystallinity region. Amazingly, a significantly even presence of a large amount of DMSO molecules in the as-
surface was obtained with the DMF/DMSO Pb−I precursor, prepared DMSO Pb−I precursor. As a mixed solvent (DMF/
which is too even to be observed from an SEM image, showing
DMSO = 9:1) was applied, the XRD pattern still presented
no obvious grain features. This even morphology was further
some diffraction peaks of PbI2(DMSO) adducts. However, the
confirmed from an AFM image, and the roughness was
diffraction peaks become much weaker, implying that the
measured to be only about 6.7 nm, much smaller than the
crystallization of PbI2(DMSO) adducts is suppressed and
above three precursors.
As observed, a significant difference in morphology was prohibited in this mixed solvent system. The FT-IR spectra in
obtained among the precursors, which suggests possible Figure 2b indicate the presence of a large amount of DMF
compositional variation. To explain this phenomenon, XRD molecules in the DMF/DMSO Pb−I precursor, which should
patterns, FT-IR spectra, and UV−vis spectra were recorded. As play a role in preventing the crystallization and growth of
presented in Figure 2a, in addition to the diffraction peaks of PbI2(DMSO) adducts. The small PbI2(DMSO) crystals or
the FTO/TiO2 substrates, DMF(H) Pb−I presents many colloidal particles would be more mobile and flexible, allowing
intense diffraction peaks at 12.7, 26.0, 28.3, 34.3, 38.7, and the formation of a compact and ultra-even Pb−I precursor film.
52.4°, which are consistent with the characteristic peak In order to highlight the difference in grain size, we
positions of PbI2. Therefore, the DMF (H) Pb−I precursor is calculated the grain size D for the different Pb−I precursors,
composed of a pure phase, high-crystallinity PbI2 crystals, and according to the Debye−Scherrer formula, D = Kγ/(B cos θ),
DMF molecules are almost non-observable from the FT-IR where K is the Scherrer constant, γ is the X-ray wavelength, B is
spectra (Figure 2b). Because no heat treatment process was the full width at half-maximum (FMHM) of the diffraction
used for the DMF Pb−I precursor, the characteristic peaks of peaks, and θ represents relevant diffraction angles. The grain
PbI2 crystals become weaker and two additional weak sizes for the DMF (H), DMF, and DMSO Pb−I precursors
diffraction peaks appear in the region from 5 to 10°. Since were calculated to be about 359, 193, and 310 nm, respectively,
the FT-IR spectra exhibit an obvious CON peak for the whereas the grain size for the DMF/DMSO Pb−I precursor
DMF Pb−I precursor, these two additional diffraction peaks in was significantly reduced to only about 59 nm. These results
30186 DOI: 10.1021/acsami.6b09925
ACS Appl. Mater. Interfaces 2016, 8, 30184−30192
ACS Applied Materials & Interfaces Research Article

Figure 3. Morphology of different MAPbI3 films fabricated from the DMF (H), DMF, DMSO, and DMF/DMSO Pb−I precursors: optical
photographs (a1−d1), SEM images (a2−d2), grain size distribution histograms (a3−d3), and AFM images (a4−d4) of DMF(H), DMF, DMSO, and
DMF/DMSO MAPbI3.

vividly confirm the presence of much smaller grains in the crystallization was obtained for the DMF Pb−I precursor,
DMF/DMSO Pb−I precursor. accompanied by a small number of PbI2(DMF) adducts. Since
UV−vis reflectance spectra were also recorded to study the DMSO has a low volatility and strong coordination with Pb2+,
different Pb−I precursors. As shown in Figure 2c, the DMF no PbI2 crystals would form in the DMSO Pb−I precursor, but
(H) and DMF Pb−I precursors exhibited a considerably higher it tends to form large PbI2(DMSO) crystals.7,39,46 When the
baseline reflectance than the DMSO and DMF/DMSO Pb−I DMF/DMSO mixed solvent was applied, DMF molecules
precursors, partially suggesting that the former two precursors thoroughly dilute the DMSO molecules. The generation of
have surfaces that are more rough. In addition, the main PbI2(DMSO) adduct crystals may terminate at the initial stage
reflectance onset for the DMF (H) and DMF Pb−I precursors after nucleation due to the limited number of DMSO
is similar at about 520 nm, consistent with the characteristic molecules. As a result, only small grains or colloidal particles
absorption onset for a crystallized PbI2 semiconductor due to were produced for the DMF/DMSO Pb−I precursor. These
its band gap of 2.3 eV, which further confirms that the main small grains or colloidal particles are proposed to stabilize and
composition is PbI2 in these two precursors. In a distinctive disperse in DMF, which favors the high mobility and flexibility
comparison, no reflectance onset at 520 nm was observed for of the Pb−I precursor that allows it to obtain an even surface.
the DMSO Pb−I precursor, but an onset at a shorter To convert the Pb−I precursors to MAPbI3, a MAI IPA/
wavelength region of about 450 nm appears, reflecting the CYHEX solution was applied, in which the addition of CYHEX
absorption property of PbI2(DMSO) adducts.36,46 Compared promotes the formation of MAPbI3 and suppresses the Ostwald
with the reflectance onset of the DMSO Pb−I precursor, a ripening process to obtain a high-quality perovskite film. Figure
slight red shift phenomenon from 450 to 470 nm is observed 3a1−d1 displays optical photographs of the MAPbI3 films
for the DMF/DMSO Pb−I precursor, which could be partially obtained from the DMF (H), DMF, DMF/DMSO, and DMSO
attributed to the quantum confinement effect of small crystals Pb−I precursors, indicating that all of the films appear dark
or colloidal particles.36 Therefore, our UV−vis results further brown after conversion. An optical photograph of all four
confirmed our above analysis of the XRD and FT-IR spectra. MAPbI3 films from a different direction (Figure S3) vividly
To better understand the above analysis, we have illustrated depicts that the DMF/DMSO MAPbI3 film is more shiny than
the features of the different film compositions in Figure 2d. the other MAPbI3 films, demonstrating a mirror-like, even
Heat treatment easily evaporates most of the DMF molecules property for the MAPbI3 film prepared from DMF/DMSO
and PbI2 strongly crystallizes, resulting in large PbI2 crystal solvent.
grains for the DMF(H) Pb−I precursor. If no post heat SEM (Figure 2a2−d2,a3−d3) and AFM (Figure 2a4−d4)
treatment process was applied, then some DMF molecules images were taken to further evaluate the surface morphologies
remain in the precursor and some would insert into the gaps of the different MAPbI3 films. Obvious cubic crystals were
between the PbI2 layers. As a result, relatively weak observed for all four MAPbI3 films. The DMF (H) MAPbI3 film
30187 DOI: 10.1021/acsami.6b09925
ACS Appl. Mater. Interfaces 2016, 8, 30184−30192
ACS Applied Materials & Interfaces Research Article

presents a lot of pinholes among the cubic crystals, and the precursors. The slower conversion for the DMF(H) and DMF
grain size ranges from dozens of nanometers to several Pb−I precursors is likely due to the difficulty of inserting MAI
hundreds of nanometers, with a mean size of 114.7 nm, molecules into the highly crystallized PbI2. This would also
which affords a roughness of 51 nm. The cubic crystal size for suppress the number of nucleation sites (known as localized
the DMF MAPbI3 film is reduced, with a mean size of 86.0 nm, nucleation) and induce the growth of large crystals,47 which
and the roughness slightly decreases to 47 nm. However, as explains the previous SEM and AFM results. The exchange
observed in the AFM image (Figure 3b4), more obvious between DMSO and MAI would promote the conversion from
fluctuations occur on the macroscale. A significantly different the DMSO Pb−I precursor to MAPbI3.7 However, the poor
morphology was observed for the DMSO MAPbI3 film. Cubic morphology of the high-crystallization DMSO Pb−I precursor
crystals are loosely dispersed with an obvious increase in the still leads to a rough MAPbI3 film with lots of pinholes. More
crystal grains, with a considerably large mean size of 147.4 nm. importantly, the exchange between DMF/DMSO and MAI not
The AFM image indicates that the surface is much rougher, only maintains the ultra-even surface morphology of the Pb−I
with the roughness increasing up to 68 nm. Amazingly, a very precursor but also promotes the conversion, allowing for a pure
compact surface is obtained for the DMF/DMSO MAPbI3 film, MAPbI3 film to be obtained.
and its grain size became smaller, with the mean size decreasing UV−vis reflectance spectra in the 300−850 nm wavelength
to 79.4 nm. The compact surface and smaller grain size led to region, as shown in Figure 4b, demonstrated much weak
an ultra-even and uniform surface with a significantly smaller reflection from 350 to 780 nm, which is identical to the light
roughness of 13 nm, as confirmed by the AFM image. absorption range of MAPbI3. The large baseline reflectance for
Obviously, the surface roughness and uniformity trends of the DMF (H) and DMF MAPbI3 indicate their relatively rough
MAPbI3 films are almost consistent with those of the Pb−I surface morphologies. DMF/DMSO MAPbI3 showed the
precursors, indicating that the Pb−I precursor has an effect on weakest baseline reflectance, suggesting that it has the most
MAPbI3 films. even surface morphology. The largest baseline reflectance was
XRD patterns (Figure 4a) were further recorded to study the obtained for DMSO MAPbI3, which is consistent with it having
compositions of the prepared MAPbI3 films. All of the MAPbI3 the roughest surface morphology, as indicated in the SEM and
AFM images in Figure 3c2,c4. Therefore, the UV−vis
reflectance spectra for the different MAPbI3 films exhibit the
same trends as the different Pb−I precursors, which further
confirms the close relation between the morphologies of the
Pb−I precursors and those of the final MAPbI3.
As demonstrated in our previous work,34 the morphology of
MAPbI3 perovskite layer greatly influences the electric contact
and charge transfer at the perovskite/carbon interface in
paintable carbon-based PSCs, which directly impacts the
performance of the cell. To evaluate the effects of perovskite
layers with different morphologies on cell performance,
paintable carbon-based PSCs were fabricated by directly
printing a commercial carbon paste on perovskite layers (as
illustrated in Figure 5a1,a2), followed by annealing at 100 °C for
60 min. In this cell structure, photogenerated electrons on the
conduction band (CB) of MAPbI3 are injected into the CB of
TiO2, whereas the holes on the valence band (VB) of MAPbI3
are extracted by the carbon electrode.
As shown in Figure S5, totally different interfacial contact
features were observed from the cross-sectional SEM images.
The more rough MAPbI3 layer exhibits a weaker interfacial
contact, and the DMF/DMSO MAPbI3 film affords a very
intimate contact with the carbon electrode. As demonstrated in
previous work, a better interfacial contact promotes more fluent
charge transfer at the interface and leads to a higher FF value
Figure 4. Composition and light absorption properties of different for C-PSCs.34 Therefore, current density−voltage (J−V) curves
MAPbI3 films: (a) XRD patterns and (b) UV−vis diffuse reflectance
spectra.
were recorded for the C-PSCs fabricated from different
MAPbI3 films, and the results are displayed in Figure 5b and
Table S1. Clearly, the photovoltic performance, especially FF
samples exhibited intense diffraction peaks at 14.1, 19.9, 24.5, values (0.61, 0.52, 0.50, and 0.66 for DMF (H), DMF, DMSO,
28.4, 31.9, 34.9, 40.6, and 50.3°, which are consistent with those and DMF/DMSO, respectively), is closely related to the
characteristic planes of MAPbI3, suggesting a high degree of evenness of MAPbI3, and the most even film, DMF/DMSO
conversion by immersing the Pb−I precursors into the MAI MAPbI3, achieves a significantly higher performance (Voc = 1.00
solution. However, there still were diffraction peaks of PbI2 at V, Jsc = 20.80 mA/cm2, FF = 0.66, and PCE = 13.71%) than
12.7° for DMF (H) and DMF MAPbI3, indicating that the that of other MAPbI3 films. As a side note, DMF MAPbI3
DMF(H) and DMF Pb−I precursors could not be completely yielded a lower FF and PCE than DMF (H) MAPbI3, although
converted. Clearly, the complete conversion of Pb−I precursors the former has a lower roughness value. This may be attributed
to MAPbI3 was achieved for the DMSO and DMF/DMSO to a more obvious fluctuation that forms on the macroscale for
Pb−I precursors, suggesting a faster conversion for these two DMF MAPbI3, which would weaken the interfacial contact with
30188 DOI: 10.1021/acsami.6b09925
ACS Appl. Mater. Interfaces 2016, 8, 30184−30192
ACS Applied Materials & Interfaces Research Article

Figure 5. Device architecture and performance of the paintable carbon-based PSCs with different MAPbI3 films. Schematic illustration of the (a1)
deposition process of the carbon electrode, (a2) cross-sectional structure, and (a3) working principle; (b) J−V curves; (c) steady PCE at voltages
close to the maximum output point (0.75, 0.75 0.60, and 0.82 V for DMF (H), DMF, DMSO, and DMF/DMSO, respectively); and (d) photovoltaic
parameter distribution for the different devices.

the carbon electrode containing macro graphite sheets (as values are around 75−95% in the absorption range of MAPbI3
shown in Figure S5). These results indicate the importance of from 400 to 760 nm, which affords a corresponding integrated
the evenness of MAPbI3, which enhances the interfacial contact Jsc of 20.23 mA/cm2, consistent with the Jsc calculated from the
and consequently the FF and PCE for C-PSCs. The IPCE J−V curve.

■
spectra in Figure S6 show a good consistency between the Jsc
values from the J−V curves, and the J−V curves with forward CONCLUSIONS
and reverse scans in Figure S7 demonstrate a higher hysteresis
We have systematically demonstrated the effects of the
for the DMSO device but a smaller hysteresis for the other precursor solvent on the composition and morphology of
devices. The steady PCE at a voltage close to the maxium Pb−I precursors and their final MAPbI3 films. The Pb−I
output point further confirms the real performance demon- precursors (with or without heat treatment) deposited from
stration from the J−V results (Figure 5c). Photovoltaic DMF solvent were mainly composed of PbI2 crystals, whereas
parameter distributions were also collected and are presented Pb−I precursors deposited from DMSO tended to generate
in Figure 5d to evaluate the performance reproducibility of the PbI2(DMSO) adduct crystals. Both PbI2 and PbI2(DMSO)
different MAPbI3 films in C-PSCs. As indicated, the more even adduct crystals demonstrated rough surfaces, resulting in rough
DMF (H) and DMF/DMSO MAPbI3 films also showed higher MAPbI3 films, which led to poor interfacial contacts with the
performance reproducibility in C-PSCs than the rougher DMF carbon electrode and low performances in paintable C-PSCs.
and DMSO MAPbI3 films. After exploiting a mixed precursor solvent (DMF/DMSO),
After preliminary optimization, the best carbon-based PbI2(DMSO) adduct colloidal particles with a small grain size
paintable PSCs fabricated from the IPA/CYHEX solvent (tens of nanometers in size) constructed the Pb−I precursor,
yielded a PCE of 14.58%, resulting from a Voc of 1.0 V, Jsc of which was more mobile and flexible, forming an ultra-even
21.83 mA/cm2, and FF of 0.67 (Figure 6a). So far, this is the surface. As a result, an ultra-even MAPbI3 film was obtained
highest reported PCE value for a carbon-based HTM-free after chemical conversion in MAI IPA/CYHEX solution, which
PSC.25−32,34,40,48 The IPCE spectrum of the best performing afforded a significantly enhanced interfacial contact with the
paintable C-PSCs in Figure 6b indicates that most of the IPCE carbon electrode and hence boosted both the FF and PCE. The
30189 DOI: 10.1021/acsami.6b09925
ACS Appl. Mater. Interfaces 2016, 8, 30184−30192
ACS Applied Materials & Interfaces Research Article

Deposition of a Carbon Counter Electrode. A commercial

carbon paste produced by Guangzhou Seaside Technology Co., Ltd.
was used for the carbon electrode, which was composed of carbon
black and graphite.32,34 The carbon paste was painted on the
perovskite layer under ambient conditions followed by heating at
100 °C for 60 min.
Characterizations. Surface and cross-section morphologies were
observed by a JSM-7500F field-emission scanning electron microscope
(FESEM). X-ray diffraction (XRD) patterns were recorded by a
Rigaku D/MAX-2500 X-ray diffractometer with Cu Kα radiation.
Diffuse reflectance spectra were measured by a UV-3000 ultraviolet
and visible (UV−vis) spectrophotometer. FT-IR spectra were
recorded by a Thermo-Nicolet Nexus 470 FTIR. Surface morphologies
and roughnesses were characterized by a Bruker Dimension ICON
atomic force microscope (AFM). Optical photographs of the samples
were taken by a digital camera (Olympus E-PL1, Japan).
A solar light simulator (Newport solar simulator, model number
6255, 150 W Xe lamp, AM 1.5 global filter) was calibrated to 1 sun
(100 mW cm−2) using a silicon reference solar cell equipped with a
KG-5 filter. The active cell area was fixed at 5 mm2 with a metal mask,
and J−V curves were recorded on an IM6x electrochemical
workstation (ZAHNER-Elektrik GmbH & Co., KG, Germany).
IPCE spectra were recorded using the IPCE kit developed by
ZAHNER-Elektrik in AC mode with a frequency of 1 Hz.

■ ASSOCIATED CONTENT
* Supporting Information
S
The Supporting Information is available free of charge on the
Figure 6. Performance of the champion device based on DMF/DMSO ACS Publications website at DOI: 10.1021/acsami.6b09925.
MAPbI3. (a) J−V curve and (b) IPCE spectrum and the corresponding SEM images and AFM images of Pb−I precursor and
integrated Jsc. MAPbI3, cross-sectional SEM images and performance
parameters of C-PSCs devices (PDF)

achieved champion PCE of 14.58% is among the highest

reported for C-PSCs. Therefore, our present work has
highlighted an effective colloidal precursor strategy to prepare
■ AUTHOR INFORMATION
Corresponding Authors
*E-mail: [email protected] (H.C.).
ultra-even perovskite layers for high-performance paintable C- *E-mail: [email protected] (S.Y.).
PSCs.

■
Notes
The authors declare no competing financial interest.

■
EXPERIMENTAL SECTION
Preparation of the TiO2 Blocking Layer and Porous Scaffold.
First, the TiO2 blocking layer was deposited on cleaned FTO glass by ACKNOWLEDGMENTS
spin-coating 0.15 M titanium diisopropoxide bis(acetylacetonate) in 1- This work was financially supported by the Young Talent of
butanol solution at 2000 rpm for 20 s; afterward, it was heated at 125 “Zhuoyue” Program of Beihang University, National Natural
°C for 5 min. Then, the TiO2 porous scaffold was spin-coated at 5000 Science Foundation 268 of China (No. 51371020), HK-RGC
rpm for 30 s using a commercial TiO2 paste (Dyesol 30 NRD, Dyesol) General Research Funds (GRF No. HKUST 606511), and the
that was diluted by ethanol at a weight ratio of 1:2.5 and heated at 100 HK Innovation and Technology Fund (ITS/004/14).

■
°C for 5 min. Afterward, the temperature was gradually heated to 550
°C and held for 2 h. After that, the TiO2 scaffold was cooled to room
temperature.32,34
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