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Ambient Air-Stable CH3NH3PbI3 Perovskite Solar Cells Using

Dibutylethanolamine as a Morphology Controller
Mira T. Z. Butt, Syed Zajif Hussain, Xuan Li, Joe Briscoe, and Habib ur Rehman*
Cite This: https://doi.org/10.1021/acsaem.0c02986 Read Online

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ABSTRACT: Hybrid inorganic−organic perovskite solar cells have gained increased attention due to their easy processing and
exceptional power conversion efficiencies. However, their limited stability against moisture, light, and heat remains an issue. Various
solution-processing techniques, particularly, additive engineering or additive-enhanced deposition, have been used to tune the
morphology of the perovskite films in order to achieve stable and high-quality films. Herein, we report the successful use of
dibutylethanolamine (DBEA) as a multifunctional morphology-controlling additive to deposit high-quality homogeneous films with
grain sizes as large as ∼5 μm under ambient processing conditions (∼50% RH). DBEA, due to its ability to donate lone pairs and to
make hydrogen bonds with the inorganic octahedra of perovskite crystals, was used to achieve a stable and uniform absorbing layer
with high efficiency compared to that of pristine or dimethyl sulfoxide (DMSO)-based perovskites. The high boiling point of this
additive also helped in achieving high efficiency by slowing down the crystallization process and increasing the crystal size to the
micron range. The best performing device with DBEA showed the highest efficiency of 11.51%, while devices prepared from DMSO
(DMSO:DMF 30:70 V/V) and without any additive (DMF only) were only 6.78 and 4.51% efficient, respectively. A similar trend
was also observed for the ambient air stability of these materials with both DBEA and additive-free devices completely degrading
within 350 h, while DBEA-incorporated devices retained ∼80% of their initial efficiency even after 525 h of ambient air storage.
KEYWORDS: perovskite solar cell, ambient air stability, nanoparticles, improved morphology, perovskite film quality

■ INTRODUCTION
Organic−inorganic hybrid perovskites have gained much
attention as sunlight harvesters because of their high carrier
mobility1 and absorption coefficient,2 tunable band gaps,3
broad absorption range,4 and excellent charge separation
properties, which has led to a power conversion efficiency
(PCE) of 25.2%.5 A key reason that perovskites function so
well in photovoltaics is their long carrier diffusion lengths,
shown to be 100 nm and 1 μm in CH3NH3PbI3 and
CH3NH3PbI3−xClx, respectively, combined with very high
absorption coefficients.5 Although highly efficient perovskite
solar cells (PSCs) have been realized, their processing still
requires tight environmental control, that is, these could only
be fabricated under an inert atmosphere or in vacuum. These
requirements impose additional cost to the fabrication of these
cells, which limits their potential for future deployment. Due to
the inherent instability of perovskite materials toward
moisture, heat, and light, even the well-formed PSCs can
undergo rapid degradation when exposed to ambient
conditions. It is therefore highly desirable to improve the
intrinsic stability of perovskite materials toward moisture to
increase their processing tolerance and their long-term
operational stability under ambient conditions.
Different methodologies such as one-step6 and two-step
depositions,7 vapor-assisted deposition,8 and solvent and
Received: December 27, 2020
Accepted: April 7, 2021

© XXXX American Chemical Society https://doi.org/10.1021/acsaem.0c02986

A ACS Appl. Energy Mater. XXXX, XXX, XXX−XXX
ACS Applied Energy Materials
additive engineering depositions9,10 have been explored to
improve the ambient air stability of PSCs. Solution-processing
methodologies, because of their ease of application, composi-
tional flexibility, and low cost, are being widely used for
depositing high-quality perovskite films on planar or
mesoporous semiconductor scaffolds. Perovskite crystal growth
directly affects the photovoltaic performance of the device;
therefore, controlling the perovskite morphology is a key to
fabricate high-quality PSCs. Perovskite morphology can easily
be tuned by cosolvents, introducing antisolvents during spin-
coating,11 vapor-induced crystallization,12 preheating the
substrates,13 and adding additives.14
The perovskite film morphology has been found to play a
key role in defining the efficiency and ambient air stability of
photovoltaic devices.15 Uncontrolled nucleation leads to rapid
crystallization and hence results in smaller crystal grains.
Smaller crystals lead to enhanced grain boundaries, which not
only impede charge transport but also act as routes for
moisture ingress.16 Thus, unchecked nucleation and crystal-
lization result in low efficiency and poor stability of resulting
photovoltaic devices. It is therefore crucial to control the
crystallization kinetics of the perovskite material to obtain
large-sized grains and pinhole-free perovskite films to limit
charge recombination and water ingress. One way to control
the nucleation and crystal growth of perovskite materials is by
incorporating additives in precursor solutions that can interact
with precursors, especially PbI2, in the solution to either
increase their solubility or reduce their reactivity.17 For this
purpose, the choice of additive becomes crucial. Various
attempts have been made to enhance the moisture stability of
these devices, which include the use of terpineol,18 phenyl-
ethylamine,19 thiols,20 polytetrafluoroethylene,21 and bilateral
amines in PSCs. These additives have been shown to passivate
the perovskite surfaces with hydrophobic groups, which
blocked water diffusion into the crystal and increased the
stability of the device under atmospheric conditions. High-
quality perovskite films with an enhanced photovoltaic
performance were obtained using Lewis bases, which form
an adduct with the perovskite precursors.22 Most of the
additives used had one functional group (amines, hydroxyl,
carbonyl, sulfonyl, etc.), which is involved in interaction with
Pb ions through coordination interaction when present on the
perovskite surfaces. However, there is a need for an additive
that has two or more reactive groups (functions as bidentate)
where both can interact with lead ions and/or with organic
cations and halide ions of the perovskite crystal to form a
cluster. Such an additive, in principle, will have a much
stronger interaction with Pb ions and therefore may not only
slow down the kinetics of the reaction but can also impart
enhanced stability to the final perovskite films. In addition, if
the additive contains multiple hydrophobic groups as well, it
would be able to better protect the perovskite films against
humidity by enhancing their hydrophobicity.
In this study, dibutylethanolamine (DBEA), due to its
multiple functionalities, was selected as a morphology
controller for methylammonium lead iodide perovskite films
because of its ability to interact and intercalate PbI2 to slow
down its reaction with methylammonium iodide (MAI) both
in solution and solid phases, and also through its two butyl
groups, it may provide greater protection against water ingress.
DBEA-incorporated films showed a much improved morphol-
ogy and surface coverage. Photovoltaic devices were assembled
from these films and their PCEs and ambient air stabilities
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were determined. Solar devices fabricated from DBEA-
incorporated perovskite films showed a much improved
morphology and surface coverage, which led to a drastic
improvement in their photovoltaic performance (PCE of
11.51%) over their pristine counterpart (PCE <4.50%) and
solvent-manipulated devices (PCE of 6.78%, with DMSO as a
cosolvent) under ambient air conditions. DBEA-incorporated
devices also exhibited much improved ambient air stabilities
compared to pristine and solvent-modified devices. Unencap-
sulated DBEA-based perovskite devices retained over 80% of
their initial performance, while pristine devices were
completely degraded in less than 350 h on exposure to
ambient conditions.
■
EXPERIMENTAL SECTION
Chemicals. F-doped SnO2 (FTO) glass, MAI, and 2,2′,7,7′-
tetrakis(N,N-di-p-methoxyphenylamine)-9,9 spirobifluorene (spiro-
OMeTAD) were obtained from Solaronix. Isopropanol (IPA,
anhydrous), titanium butoxide, dyesol(R) 18NR-T titania paste,
lead iodide, dimethylformamide (DMF), DBEA, dimethyl sulfoxide
(DMSO), lithium bis(trifluoromethylsulfonyl)imide (LiTFSI), and 4-
tert-butylpyridine (TBP) were purchased from Sigma-Aldrich and
were used as received.
Device Fabrication. The PSC fabricated in our laboratory had
the following structure: FTO/c-TiO2/m-TiO2/perovskite/spiro-
OMeTAD/Au. Fluorine-doped tin oxide (FTO) glass was cleaned
with a detergent and sequentially sonicated with distilled water,
acetone, and IPA in an ultrasonic bath for 30 min each. After N2 blow-
drying, FTO glasses were placed in a UV cleaner for 30 min to
remove any organic residues. In order to get the required electrode
pattern, the FTO substrates were etched with Zn powder and 1 M
HCl solution. A 50 nm compact titania layer was deposited on the
etched FTO glass substrates by spin-coating a 5 wt % solution of
titanium butoxide in IPA at 3000 rpm for 30 s followed by annealing
at 500 °C under an ambient atmosphere for 1 h. In order to further
improve the connection between compact and mesoporous titania,
the compact titania-coated substrate was dipped in 40 mM aqueous
solution of TiCl4 at 70 °C for 30 min. Afterward, the substrate was
heated at 450 °C for 30 min. The mesoporous titania scaffold layer
was spin-coated at 4000 rpm with diluted dyesol (R) 18NR-T titania
paste in ethanol. To prepare titania solution, 1 g of titania paste was
dissolved in 5 mL of ethanol by sonication and stirring for multiple
times. The coated substrates were again calcined at 500 °C for an
hour.
The perovskite layer was deposited onto mesoporous titania under
ambient conditions (approximately 50% relative humidity) according
to the following method: 0.462 g of PbI2 and 0.15 g of MAI were
dissolved in 1 mL of DMF at 70 °C. This solution was filtered using
0.2 μm PTFE syringe filters. To the filtered precursor solution, an
optimized amount of DBEA was added under stirring. The solution
was spin-coated at 3000 rpm for 30 s and then the coated substrate
was dried at 100 °C for 10 min. The cooled substrate was dipped in
0.01 g of MAI in 1 mL of IPA solution for 30 s to improve perovskite
formation and surface restructuring. The substrate was dipped for 30 s
after which it was spun at 3000 rpm for 30 s resulting in a color
change from light to dark brown. At this stage, the speed was reduced
to 500 rpm for 2 s during which 0.5 mL of chlorobenzene as an
antisolvent was added. The substrate was again spun at 3000 rpm for
30 s to remove excess solvents and allow the formation of perovskite
crystals. Finally, the film was heated at 115 °C for 20 min to ensure
complete conversion to perovskites. DMSO-modified films were
prepared in the same way as of no-additive films except that 30% of
DMF was replaced by DMSO in a no-additive solution.
The hole transporting layer solution was prepared and coated
following the reported method.7 Typically, 72.3 mg of spiro-
OMeTAD along with some additives was dissolved in 1 mL of
chlorobenzene. The additives include 28.8 μL of TBP and 17.5 μL of
LiTFSI (450 mg in 1 mL of acetonitrile). The resulting solution was
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spin-coated on the perovskite film at 3000 rpm for 30 s and then dried
at 60 °C for 10 min. Finally, 100 nm gold was thermally evaporated as
a back contact on the top of the device with 100 nm thickness to
finish the device fabrication.
Characterization. The morphology of the perovskite crystals was
characterized using an FEI Inspect F field emission scanning electron
microscope. The J−V curves were measured with a Keithley 2400
source meter under simulated AM 1.5G solar light irradiation from a
solar simulator from Newport (Class ABB) and in the dark. The
intensity of the solar light illumination was measured using a standard
silicon cell. The incident photon-to-electron conversion efficiency
(IPCE) spectra of the device were measured using a Zahner PP211
electrochemical workstation. The UV−vis spectra were obtained using
a PerkinElmer Lambda 950 UV/vis spectrometer.
■ RESULTS AND DISCUSSION
Deposition of high-quality perovskite films is a key to the
successful realization of high efficiency and stable PSCs.
Perovskite materials undergo rapid hydrolyzation to their
respective precursors on exposure to ambient air conditions. It
is therefore very challenging to fabricate and operate PSCs in a
humid environment, which limits their potential for wide-
spread deployment. One of the major issues with perovskite
layer quality is the rapid nucleation and crystallization of PbI2,
which leads to gross phase separation when a solvent is
evaporated during the film formation process. It is therefore
very important to control the growth kinetics of PbI2 crystals
during film deposition. Among the strategies explored to
control PbI2 kinetics, solvent engineering and additive
engineering have attracted widespread interest. In solvent
engineering, a solvent that has the ability to intercalate into the
PbI2 crystals is used to help retard crashing out of PbI2 from
the solution during film formation. Additive engineering, on
the other hand, uses organic molecules with appropriate
hydrophilicity and hydrophobicity that improve film properties
by chemically interacting with precursors, reducing pinholes,
and passivating grain boundaries while limiting moisture
ingress into the perovskite films. In this study, DBEA was
selected as a multifunctional additive due to its unique
molecular structure. Unlike most additives, DBEA has two
hydrophilic groups (amine and hydroxyl) and two hydro-
phobic chains. It is therefore expected that its two hydrophilic
groups may interact strongly with Pb ions (to form bigger
clusters), while its hydrophobic chains (butyl groups) will
increase the solubility of well-coordinated Pb ions in a
commonly used solvent. To verify these assumptions, we first
prepared PbI2 solutions with and without DBEA in a DMF
solvent under ambient atmospheric conditions. For compar-
ison, we also prepared a PbI2 solution using DMSO, one of the
widely employed solvents for solvent engineering of perov-
skites. Films were deposited on glass substrates through spin-
coating and were heated at 100 °C for 10 min before
characterization. The top-surface scanning electron microscopy
(SEM) images of deposited films from these solutions are
shown in Figure S1. It is clear from Figure S1A that the film
deposited without an additive resulted in gross phase
separation where crystals up to tens of micrometers could be
seen. This result can be linked to the uncontrolled nucleation
and crystallization of PbI2 during film deposition in line with
earlier reports.7 The morphology of DMSO-deposited films
(Figure S1B) shows that DMSO significantly reduced the
crystal size and improved surface coverage. However, there
were still some areas with incomplete coverage. It is well
known that DMSO intercalates into PbI2 crystals to form a
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stable adduct (PbI2(DMSO)2), which significantly retards
phase separation during solvent evaporation.9,10,23 A highly
compact, uniform, and pinhole-free film was observed (Figure
S1C) when a small amount of DBEA was added into the DMF
solution of PbI2. This improvement can be linked to the
enhanced interaction of DBEA with Pb ions through its two
electron-donor groups (amine and hydroxyl). Enhanced
interactions of DBEA with PbI2 would be expected to lead
to a greater retention of increased amount of carbon in the
final film. Figure S2 shows the EDS graphs of these films along
with percentages of carbon, iodide, and lead in each film. The
amount of carbon increased from 11.28 wt % for the control
film to 14.04 wt % for the DMSO-deposited film. However, the
DBEA-incorporated film showed the highest amount of carbon
(34.09 wt %), which can be linked to its enhanced interaction
with PbI2. To confirm that DBEA forms a stable adduct with
PbI2, X-ray diffraction (XRD) spectra of these materials were
recorded and are shown in Figure S3. As expected, no adduct
peak could be observed for the control sample. Although
adduct diffraction peaks were observed for both DMSO- and
DBEA-incorporated PbI2, the adduct peak is much smaller for
DMSO. Moreover, DMSO-intercalated PbI2 also exhibited a
strong peak corresponding to the (001) plane of PbI2, while no
such peak could be seen for the DBEA sample. This further
reinforces the fact that DBEA with its bidentate functionalities
interacts strongly with PbI2. In addition, the two electron-
donating groups on DBEA can also interact with more than
one Pb ions forming small clusters. The particle size
distribution (Figure S4) of the DBEA-incorporated solution
confirms that the average particle size for this solution is the
largest (>350 nm) compared to those of DMSO (∼220 nm)
and no-additive (∼80 nm) solutions. Since one DBEA
molecule can be coordinated with more than one Pb ions in
solution to form clusters and every DBEA molecule in these
clusters has two butyl groups, therefore, DBEA-coordinated Pb
ion clusters would have significantly higher solubility in aprotic
solvents than pure or DMSO-intercalated PbI 2. More
controlled nucleation and growth kinetics along with enhanced
solubility of DBEA-incorporated PbI2 solutions resulted in
much improved films with no pinholes. The above discussion
clearly demonstrates that DBEA can be successfully employed
as an additive for depositing high-quality perovskite films.
Next, we investigated the impact of DBEA incorporation on
the fabrication of CH3NH3I-based PSCs under ambient
conditions. In this study, we used CH3NH3PbI3 as a
representative example because (1) it is the most widely
investigated system and (2) it has greater sensitivity to ambient
conditions.
In an additive engineering approach, amine-functionalized
organic molecules having appropriate hydrophobic properties
are coated on top of perovskite films and/or added into the
precursor solutions to form a water insulating layer. The
hydrophilic part (like amine groups) of the additive has been
shown to anchor to undercoordinated Pb ions or defects sites
on perovskite surfaces or grain boundaries, while the
hydrophobic end forms a moisture-resistant barrier and limits
water ingress through these defects.24,25 Depending upon the
structure of these additives, they can also enhance the
solubility of PbI2, which can lead to improved film properties.
Herein, we demonstrate that DBEA can be effectively used
as a morphology controller to deposit dense and high-quality
MAPbI3 perovskite films under ambient conditions. The
chemical structure of DBEA along with the film deposition
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Figure 1. (A) Schematic of the deposition process for DBEA-added perovskite films and (B) mechanism of DBEA intercalation and defect
passivation of perovskite surface defects. Morphology evolution during the deposition process in DBEA-incorporated perovskites, (C) as-deposited
films, (D) after soaking in MAI/IPA solution, and (E) after chlorobenzene wash.
process is illustrated in Figure 1A. DBEA has two functional
groups, one amine group and one hydroxyl group, and two
main hydrophobic tails (butyl groups). Lone pairs on both
oxygen and amine groups can interact with 6p orbitals of
undercoordinated Pb ions on the surface or defect sites to
passivate the surface and grain boundaries, while the hydroxyl
group can engage through hydrogen bonding with iodide ions
to further enhance the stability of these films.24 Nitrogen on
DBEA can also provide additional protection to perovskite
surfaces by replacing its A-site vacancies at the surface and
grain boundaries.23 Since the concentration of additives plays a
major role in determining the quality of the final film, we
therefore first studied the influence of DBEA concentration on
the morphology of perovskite films.
We used methylammonium lead iodide (MAPbI3) to
optimize the DBEA amount in precursor solutions. Different
concentrations of DBEA were directly added to perovskite
precursors and perovskite films were deposited by spin-coating
followed by dipping in CH3NH3I in IPA and chlorobenzene
washing. The surface morphologies of films with different
concentrations of DBEA are shown in Figure S5. In the
absence of any additive or intercalating solvent, the control
film under ambient conditions exhibited gross phase separation
due to uncontrolled reaction kinetics between lead iodide and
MAI. With the increasing DBEA content, the morphology
changed from uniform but porous (3 wt %) to very compact
and highly uniform (9 wt %) to grossly segregated (14 wt %).
Increasing the amount of DBEA improved the film quality of
CH3NH3PbI3 by controlling the nucleation and growth
kinetics of perovskite formation and improved the solubility
of precursor solutions. Gross separation for the 14 wt % sample
may be due to the self-assembly of DBEA in DMF solvent,
which leads to segregated perovskite structures. The J−V
curves of solar devices based on these films are shown in
Figure S6. This data follow a similar trend as observed in SEM
studies, and the best performance was observed for the 9 wt %
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device. All further studies in this work were therefore
performed with this optimized amount of DBEA (9 wt %).
All fabrication, storage, and testing of PSC devices were
performed under ambient air conditions (∼50% relative
humidity). CH3NH3PbI3 films were prepared with the
optimized concentration of DBEA using the modified
antisolvent engineering method as shown in Figure 1A (refer
to the Experimental Section for a detailed fabrication
procedure). Control films (with no additive) were deposited
using a two-step deposition process, while DBEA-incorporated
films (where DBEA was directly added to the MAI and PbI2
precursors in DMF) were initially dipped in MAI solution in
IPA followed by a chlorobenzene (CBZ) wash. DMSO-
incorporated films were prepared by replacing 30% DMF with
DMSO in an additive-free solution (no additive). Analyzing
the DBEA-added films at each stage of this process showed
that the as-deposited films were highly uniform (Figure 1C)
but with no appreciable perovskitelike color. This is due to the
stronger interaction of DBEA with Pb ions, which significantly
slows down the molecular exchange between DBEA and MAI.
To improve the perovskite formation, these films were soaked
in MAI solution. Soaking of DBEA-incorporated perovskite
films in IPA solution significantly changed their morphology
from smoother and uniform to much rougher and highly
porous (Figure 1D). This clearly shows that DBEA-
incorporated films have higher solubility even in IPA. CBZ
wash once again changed the morphology of these films from
rougher and porous to a compact, dense, and highly uniform
film with very large grain sizes (Figure 1E). The films turned
from light grayish/brownish to dark reddish black. This
transformation could be explained by the improved dissolution
and recrystallization of the DBEA-incorporated perovskite film
by CBZ. The surface morphologies of optimized perovskite
films fabricated without and with DBEA are shown in Figure
2A,2C. Due to the use of ambient processing conditions,
having high relative humidity (>50%), control films exhibited a
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ACS Applied Energy Materials
Figure 2. Surface morphologies of MAPbI3 perovskite films fabricated
(A) without additive, (B) with DMSO (with a DMF/DMSO ratio of
70:30), and (C) with DBEA. Panels (D−F) show water contact
angles for perovskite films without additive, with DMSO, and with
DBEA, respectively. Films without additive and with DBEA are
prepared from DMF.
dendritic morphology resulting from very small grains lining
the large PbI2 crystals (Figure 2A). This result is consistent
with earlier reports on the synthesis of MAPbI3 perovskites
when ambient moisture levels were not controlled.26 Films
from the DMSO-modified solution showed a compact and
dense film with few pinholes that result from reasonably
controlled crystallization during the solvent evaporation stage
(Figure 2B). As physically intercalated DMSO molecules in
PbI2 can easily evaporate during the drying stage, they
therefore offer a limited control over phase separation during
the film formation process. The DBEA-incorporated film, on
the other hand, showed a much more uniform and denser
microstructure with grain sizes over 5 μm (Figure 2C). These
grain sizes of over 5 μm are among the highest, to our
knowledge, for additive-modified perovskite films (see Table
S1). These large and uniform grain sizes improved the film
quality and morphology, which can be attributed to the ability
of DBEA to regulate reactions between MAI and PbI2 during
perovskite formation. The growth of larger grain-sized crystals
can be attributed to the ability of DBEA to form highly soluble
PbI2−DBEA−MAI clusters by linking many Pb ions together
(Figure 1B). These clusters can form a uniform film due to
their higher solubility in DMF. MAI soaking restructures these
films by enabling exchange of some amount of DBEA with
MAI molecules (Figure 1D). CBZ wash helps to complete
DBEA exchange with MAI as DBEA has higher solubility in
CBZ than in MAI. During this recrystallization process, smaller
perovskite clusters will interact with neighboring crystals
forcing them to fuse together to form a large crystal grain.
During this process, the DBEA molecules will move to the
surface or/and grain boundaries and through their interaction
with uncoordinated lead ions and defects sites on surface or
grain boundaries, they help alleviate/passivate these defects.
Additionally, the nitrogen in DBEA may also replace A-site
vacancies on the perovskite surface, which may lend additional
stability to the perovskite structure.23 The two butyl groups on
each DBEA molecule will impart strong resistance to water
ingress when attached onto the surface and grain boundaries of
the perovskite. This is clearly visible from an increased contact
water angle from 61−63° for control perovskite to 76−78° for
DMSO-modified and to 92−94° for DBEA-incorporated films
(Figure 2D−F). This demonstrates that DBEA not only
passivates defects and reduces grain boundaries (by increasing
the grain size) but also insulates the film surfaces and grain
boundaries from unwanted water ingress. This also confirms
that by adding a small amount of DBEA to the CH3NH3PbI3
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precursor solution, compact, highly uniform, and moisture-
resistant films can directly be deposited under ambient air
conditions which otherwise would not be feasible.27
As discussed above, DBEA has two electron-donating
groups, that is, amino and hydroxyl, where both can interact
with Pb ions in the perovskite precursor solution.23,24 In
addition to the direct interaction of the hydroxyl group with Pb
ions, it can also engage with the iodide ions of PbI2 octahedra
through hydrogen bonding. This raises the possibility that the
DBEA molecule, through its unique structure, can engage with
more than one octahedra of PbI2 and can lead to clusters of
various sizes. To test this assumption, the particle size
distribution of the DBEA-incorporated perovskite solution
was determined using a Zetasizer. Figure 3 shows the plot of
Figure 3. Size distribution of PbI2−DBEA−MAI and PbI2−DMSO−
MAI adduct clusters in precursor solutions compared to a pristine
device containing no additive.
the particle size distribution of PbI2−DBEA−MAI adduct
clusters in a solution having the optimized concentration of
DBEA. It is clear from these curves that the precursor solution
having no additive has much smaller particles with a narrow
size distribution (average particle size of 223 nm), while the
DMSO-modified solution has a broader distribution with
cluster sizes ranging from 300 nm up to 1 μm. A drastic change
in the particle size was observed for the DBEA-incorporated
solution where the average size reached ∼4 μm with some
clusters exhibiting sizes as large as 8 μm. These results back our
assumption that DBEA can interact with multiple Pb ions in
solution to form clusters of different sizes and that these
clusters define the morphology of the final film. These results
are in agreement with those of SEM and XRD of DBEA-
incorporated PbI2.
The above results confirm that DBEA strongly interacts with
Pb ions both in solution and in the solid state. These
interactions can be explained on the basis of an acid−base
reaction where the nitrogen and oxygen on the DBEA additive
act as Lewis bases, while the Pb ion acts as a Lewis acid. To
understand these interactions, the Fourier transform infrared
(FTIR) spectra of PbI2 mixed with DBEA and control and
DBEA-incorporated perovskites are shown in Figure 4 and
Figure S7. Figure 4A shows that the C−N peak not only
shifted from 1127 to 1052 cm−1 but also broadened when an
equimolar amount of DBEA was mixed with PbI2, which
confirms the influence of N on DBEA in adduct formation with
PbI2. Previous studies have shown that amine or hydroxyl
containing molecules can readily interact with exposed iodide
ions in the perovskite through strong hydrogen bonding.28,29
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Figure 4. FTIR spectra of (A) mixture of DBEA with PbI2 dried at 25 °C showing the displacement of the respective peaks in the PbI2−DBEA
adduct and (B) MAPbI3 perovskite with and without DBEA in the 1300−1600 cm−1 region.

Figure 5. XRD spectra of MAPbI3 perovskites deposited without any additive, with DMSO, and with DBEA as an additive dried at 60 °C overnight
in vacuum (A) and magnified peaks between 10 and 13.5° (B).

Organic molecules (terpineol) with hydrophobic groups have
been used to passivate perovskite surfaces and improve their
moisture stability due to the water-repellent nature of
hydrophobic moieties.30 Figure S7 shows that the spectra of
both control and DBEA-incorporated perovskites are very
similar except in the 3500 cm−1 region, where the DBEA-
incorporated perovskite shows a weak peak around 3400 cm−1
while the control perovskite spectra has no such peak. This
broad peak around 3400 cm−1 starting from 3550 cm−1 and
extending up to 3250 cm−1 can be linked to the strongly
hydrogen-bonded hydroxyl groups in the DBEA-incorporated
perovskite. The presence of a broadened peak here shows that
a small amount of DBEA is still present in the final perovskite
film and that the hydroxyl group of DBEA strongly interacts
with some other groups in the perovskite. Figure 4B shows the
FTIR spectra of both control and DBEA-incorporated
perovskites from 1300 to 1600 cm−1. It is clear from this
plot that there is no discernable change in the NH3 bending
peak (1464 cm−1) for both perovskite films, confirming that
there is no residual DBEA left in the bulk of the perovskite.
The appearance of a small CH3 stretching peak at 1380 cm−1
confirms the presence of a trace amount of additive in the
perovskite layer, which may be present on the surface and grain
boundaries.
In order to understand how crystallization in control,
DMSO-modified, and DBEA-added perovskite solutions
evolves during the film deposition process, XRD was
performed on these perovskite films before and after perovskite
formation. Figure 5A shows the XRD patterns of the perovskite
films dried at 60 °C overnight under ambient conditions. In
F https://doi.org/10.1021/acsaem.0c02986
the case of DMSO-modified and DBEA-incorporated films, an
adduct peak was observed around 11.15° (Figure 5B), which is
linked to the interaction of amine and/or hydroxyl groups of
DBEA with Pb ions in agreement with the Zetasizer results,
while a peak corresponding to pure PbI2 (12.81°) was only
visible for a sample with no additive. This supports earlier
results that DBEA strongly interacts with PbI2 to form a stable
adduct; therefore, no free PbI2 will be available in the additive-
incorporated sample, while the perovskite without DBEA is
very sensitive to moisture and can easily be degraded to PbI2
when exposed to moisture/water vapors.
To understand the influence of DBEA on the crystal
structure of perovskites, XRD analysis was performed on
perovskite films heated at 115 °C for 20 min. Figure 6 shows
the XRD patterns of the perovskite films fabricated with and
without the use of DBEA and DMSO. These perovskites when
heated at 115 °C exhibited no adduct peak, which confirms
that the additive does not hamper perovskite crystallization.
The main characteristic CH3NH3PbI3 peaks are present in
both pristine and additive-assisted perovskite films. The peaks
at 14.11, 28.48, 31.61, and 43.18° are assigned to the (110),
(220), (310), and (330) planes, respectively, which confirmed
the tetragonal phase of perovskite crystals.31 No shift in peaks
for DMSO-modified or DBEA-incorporated spectra relative to
that of control film was observed, which confirms that DMSO
and DBEA do not alter the crystal structure of the resulting
perovskite layers. The PbI2 peak at 12.54° can clearly be seen
in both pristine and DMSO-modified perovskite films, which
shows that the precursors in these materials are either not fully
converted into perovskites or degradation has already occurred
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ACS Applied Energy Materials
Figure 6. Thin-film XRD patterns of CH3NH3PbI3 perovskites
realized without any additive and with DMSO and DBEA as an
additive recorded after heating these films at 115 °C for 20 min.
during annealing under ambient conditions.32 It has been
shown in earlier studies that organic−inorganic perovskites
undergo rapid degradation when heated under ambient
conditions.33 Water in air weakens the interactions between
cations and halide ions due to the greater polarity of water,
which leads degradation of perovskite structures to methyl-
amine, HI, and PbI2. On the other hand, no such peak was
visible in the additive-based perovskite, which suggests that the
enhanced hydrophobicity of DBEA helps in reducing water
ingress, which in turn retards its moisture-induced degradation.
In addition, the amine in DBEA also helps in completely
converting the precursors into perovskite crystals and hence
improves crystallization. Moreover, the stronger peak intensity
of the (110) peak in the DBEA-incorporated film is due to the
preferential orientation of the CH3NH3PbI3 perovskite film
along the (110) plane. The (110) plane has been shown to be
less prone to crystal/grain boundary defects.25 Therefore, the
addition of DBEA not only improves the crystal quality and
limits degradation but also reduces crystal and grain boundary
defects due to the larger grains, resistance to water ingress, and
preferred orientation.
The optoelectronic properties of the MAPbI 3 films
fabricated using DMSO and DBEA were measured using a
UV−vis spectrophotometer, and the results are shown in
Figure 7. The UV−vis spectra show the typical absorption
spectra for the CH3NH3PbI3 perovskite with absorption of the
film between 300 and 800 nm, which can be attributed to its
band gap of 1.55 eV. It can be inferred that the optical
absorption of the films was enhanced across the whole visible
region of the electromagnetic spectrum when DBEA was used
Figure 7. UV−vis spectra of CH3NH3PbI3-absorbing layers fabricated
with DMSO and DBEA in comparison to the pristine layers
containing no additive.
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compared to DMSO and pristine CH3NH3PbI3. This increase
in the absorption was due to the improved crystal quality and
surface coverage, which was significant for the DBEA-added
film. Since the perovskite crystals were not homogeneously
distributed on the mesoporous titania, the optical absorption is
much lower for the perovskite film fabricated without any
additive. Also, previous studies have shown that the decrease in
the perovskite crystal size decreases the absorbance of the
perovskite film, which in turn is related to the higher
reflectance values of these films.34
The radiative recombination of electrons and holes results in
the emission of energy in the form of photoluminescence (PL).
A high PL intensity on nonconductive substrates indicates
more radiative recombination, whereas the reduction in the
emission intensity reveals the extent of nonradiative recombi-
nation occurring in the system. Depending upon the
deposition process, two types of defects can be formed in
the perovskite layers: (1) deep defects that are formed when
iodide ions replace Pb or MA sites in the crystal lattice and (2)
shallow defects that are formed due to the stoichiometric
imbalance at the surfaces.35 They both contribute to
nonradiative losses in PL; however, the contribution of deep
traps to PL losses is significantly higher than that of shallow
traps. These defects strongly correlate with the crystal quality
and grain sizes.36 Figure 8A shows the comparison of the PL
spectra of DMSO- and DBEA-modified perovskite layers with
that of a pristine layer prepared on bare glass slides. It is clear
from the PL plot that the DBEA-incorporated perovskite layer
exhibited the highest intensity whereas the pristine layer
showed the lowest intensity. The PL of the DMSO-modified
layer showed an intermediate response. The main reason for
the higher PL intensity in the case of DBEA layer on glass
substrates can be linked to the fewer defects (especially deep
defect states) due to controlled crystallization and large grain
sizes in these films.37,38 The DMSO-added layer showed an
intermediate behavior, which can be linked to better film
formation and film quality compared to the pristine film. If,
however, films are deposited on charge transport layers, their
emission intensities are drastically reduced. The quenching of
intensity in these films indicates an effective charge transfer
from the active layer to the charge transport layer (TiO2) and
it is linked to efficient mobility of charges in these films. The
lower the PL intensity, the higher the charge mobility and the
lower the defect sites in the films. Figure 8B shows the PL
spectra of both pristine and DMSO-modified and DBEA-
incorporated perovskite films deposited on mesoporous TiO2
at a 400 nm excitation wavelength. The PL peaks are centered
at around 775 nm in all films, which corresponds to a near
band-to-band (B−B) recombination across the optical band
gap of the perovskite.39 The decrease in the PL intensity can
clearly be seen in the films made with DMSO and DBEA
compared to a pristine perovskite layer. However, the decrease
is not as pronounced in the case of DMSO-modified films
compared to the DBEA one. This can be attributed to a more
effective charge transfer from the DBEA-incorporated perov-
skite film to the TiO2 layer compared to that of the DMSO or
control layer. The diminished PL intensity in the case of
DBEA-incorporated films is a consequence of improved film-
forming characteristics of DBEA, which results in larger crystal
grain sizes and dense and compact layers that are free from
defects and pinholes. To understand the strong quenching
behavior of DBEA-incorporated films deposited on conducting
substrates, we studied the charge dynamics of solar devices
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Figure 8. PL spectra of the CH3NH3PbI3 perovskite films fabricated on (A) bare glass slides and (B) mesoporous titania deposited on FTO
without additive and with DMSO and DBEA measured at a 400 nm excitation wavelength.

using electrochemical impedance spectroscopy (EIS). The

transport data extracted from fitted Nyquist plots show that
DBEA-incorporated devices have about nine times lower
charge transport resistance (103.2 Ω compared to 906.1 Ω),
about four times higher recombination resistance (558.6 Ω
compared to 128.7 Ω), and an order of magnitude higher
carrier lifetimes (τ = 0.59 ms compared to τ = 0.06 ms)
compared to the pristine devices. We believe that the enhanced
film quality and greater passivation of defects in DBEA-added
films lead to lower charge transfer and higher recombination
resistance that enables greater charge extraction in these films,
which significantly increases their PL quenching.40,41 This
result corresponds well with the morphology, XRD studies,
and EIS results discussed in the relevant sections. However,
there is a small intensity still visible that may be due to the
presence of some hydrated PbI2 that is formed under higher
moisture conditions and leads to nonradiative recombination
due its insulating nature.
To test whether the improved morphological, structural, and
optical characteristics of additive-incorporated films can also be
translated to an enhanced photovoltaic performance of
corresponding solar devices, solar cell devices from films
with no additive and with DMSO-modified and DBEA-
incorporated solutions were fabricated with an n−i−p
configuration (FTO glass/c-TiO2/m-TiO2/perovskite/spiro-
OMeTAD/Au). Photovoltaic parameters (short-circuit current
(Jsc), open-circuit voltage (Voc), fill factor (FF), and PCE) are Figure 9. PV performance of CH3NH3PbI3 perovskites, (A) J−V
strongly dependent on the quality, morphology, and curves of best devices and (B) statistical data of various PV
crystallinity of the absorber layer. The J−V curves for the parameters calculated from 30 devices (10 for each group) fabricated
best devices fabricated with DMSO-modified and DBEA- with and without DBEA and with DMSO.
incorporated absorber layers and additive-free pristine films are
shown in Figure 9A, while the statistical average data of Table 1. PV Parameters for PSCs with and without DBEA
photovoltaic (PV) parameters for a set of 10 devices are shown and DMSO Additivesa
in Figure 9B and Table 1. It is clear from Figure 9A that the
additive Jsc (mA/cm2) Voc (V) FF η (%)
pristine device shows a very low PCE of 4.510% because of its
low value of Jsc of 710.53 mA/cm2, a Voc of 0.75 V, and an FF No 7.71 ± 2.75 0.71 ± 0.03 0.45 ± 0.06 3.41 ± 0.86
DMSO 12.30 ± 1.34 0.77 ± 0.06 0.48 ± 0.04 5.25 ± 0.96
of 0.569, while the DMSO-incorporated device exhibited an
DBEA 21.23 ± 0.74 0.93 ± 0.01 0.54 ± 0.03 10.55 ± 0.68
improved Jsc of 14.78 mA/cm2, a Voc of 0.82 V, and an FF of
best 10.517 0.75 0.564 4.45
0.564. In contrast, the best DBEA-incorporated device showed control
a 236% increase in PCE (11.51%). This enhancement was cell
mainly due to its much improved Jsc (21.61 mA/cm2), Voc best cell 14.78 0.82 0.560 6.78
(0.92 V), and FF (0.5924), which all made substantial with
DMSO
contributions. The PCE values of 30 devices (10 each with best cell 21.23 0.92 0.594 11.51
and without an additive and a modifier) are shown in Figure with
9B, while all the corresponding PV parameters of these devices DBEA
a
are listed in Tables S2 and S3. It is clear from Figure 9B and Each value of these parameters is the average of data taken from 10
Tables S2 and S3 that DBEA-incorporated devices not only devices. The table also lists the I−V data from our best working cells.
exhibited much improved PV performance but also showed
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ACS Applied Energy Materials
remarkable reproducibility. This clearly demonstrates the
effectiveness of this process for fabricating high-quality
perovskite films under relatively high humidity conditions.
The PV parameters of these devices show a clear correlation
with the morphology of resulting perovskite films, with the
most grossly phase-separated layer showing the worst perform-
ance.
Devices made from DBEA resulted in compact and defect-
free perovskite films with large-sized grains and much
improved crystal quality. Dense, pinhole-free, and highly
crystalline films with larger grains led to a significantly higher
optical absorption and PL, which are critical to improving the
Jsc and Voc of these devices.
The poor performance of pristine and DMSO-modified
devices can be linked to the poor film-forming properties of
MAPbI3 in a high moisture environment. Since water has
stronger interactions with halide ions of the perovskite
octahedra, therefore, under high relative humidity conditions,
the perovskite undergoes rapid degradation to hydrated PbI2.
Hydrated PbI2 rapidly precipitates during spin-coating due to
its lower solubility in DMF, leading to a highly nonuniform
film with large number of grain boundaries. Grain boundaries
and uncoordinated sites on these crystals act as defect sites for
electron−hole recombination. The low optical absorption
coupled with large traps for charge carriers result in poor PV
performance of the control devices. The enhanced PV
performance of DBEA-incorporated devices can be linked to
a number of parameters such as high optical absorption,
improved morphology, and film quality. Highly dense films
with micrometer-sized grains were deposited from a DBEA-
added perovskite precursor solution under high humidity
conditions. Large grains resulted in a pinhole-free, uniform,
and highly smooth surface, which exhibited high absorption
and significantly reduced grain boundaries. The full width at
half maximum values of the (110) peak for films with DBEA,
DMSO, and without additive are 0.090, 0.157, and 0.226°,
respectively, which highlights the high quality of crystals in
DBEA-incorporated films. Thus, the DBEA-added film has
higher crystallinity and larger crystal sizes with much reduced
grain boundaries compared to pristine or DMSO-added films.
Defects sites on the surface and grain boundaries were further
passivated through interactions of these defect sites and/or
replacement of A-site vacancies with hydrophilic substituents
of DBEA, thus further reducing the charge trap sites on these
films. Thus, uniformity and quality of the DBEA-added film
with larger grains and crystal sizes and much reduced defect
sites lead to high optical absorption, greater charge generation,
and charge transport in these films, which lead to the drastic
enhancement in their PV performance.
Although DBEA addition led to drastic improvements in
both Jsc and Voc in these devices, however, only a limited
improvement in FF could be observed. The presence of a small
amount of hydrated PbI2, resulting from moisture exposure of
these films during film deposition, insulates interfaces and
grain boundaries to inhibit charge collection, which leads to
nonradiative recombination.42 Although the formation of
hydrated lead is drastically reduced when using our additive,
it cannot be fully eliminated. This nonradiative recombination
leads to lower Voc, which adversely impacts the FF. Most
devices prepared under an inert atmosphere exhibit Voc well
over 1 V. In our case, however, the maximum Voc is around 930
mV, which still is on the lower side despite a larger grain size
morphology and much reduced traps/defect sites. We believe
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there is a possibility that small gaps/holes may be present
along the grain boundaries where a small amount of hole
transport material may penetrate to interact with titania. These
regions may act as pathways for recombination, especially at a
higher potential. This could also explain the possible reason for
low Voc and low FF for these devices, which are limiting the
overall performance.
The incident photon-to-electron conversion efficiency
(IPCE) spectra (Figure 10) revealed the increased efficiency
Figure 10. Incident photon-to-electron conversion efficiency (IPCE)
curves of solar devices fabricated with no additive and with DMSO
and DBEA along with their respective integrated current densities.
for DBEA compared to DMSO or pristine perovskites across
the whole absorption range (400 to 700 nm). The addition of
amine in the precursor solution controls the crystallization rate
and thin-film formation of perovskites. This higher efficiency
can be explained by the pinhole-free perovskite film leading to
uninterrupted charge extraction. Due to the poor light
harvesting and charge extraction ability of the pristine
perovskite, the IPCE efficiency was low at longer wavelengths.
This trend exactly matched the J−V curves of these devices.
The integrated current density was calculated from the IPCE
data shown in Figure 10. The values of current densities are
completely in accordance with the values obtained from the J−
V curves. The onset of the photocurrent at around 700 nm was
in line with the previous perovskite reports due to the expected
band gap of CH3NH3PbI3.43 The high current density for
DBEA can be explained on the basis of the improved crystal
quality and the defect-free sensitizer film without any pinholes,
which provided an uninterrupted pathway for electron
conduction and transfer to the external circuit. On the other
hand, the reduced current values for both DMSO-modified
and control devices were caused by reduced optical absorption
as shown by UV−vis analysis, increased series resistance, which
impeded the electron transfer to the conduction band of titania
as shown by PL above, as well as high recombination caused by
the large amount of the PbI2 secondary phase.
To further explore the improved performance of DBEA-
incorporated devices compared to that of DMSO or no-
additive devices, EIS spectra of these cells were measured at
room temperature and their Nyquist plots are shown in Figure
11. These spectra were fitted using a standard equivalent
circuit shown as an inset in Figure 11. The fitted curves are
shown in Figure S8, while the extracted EIS parameters are
listed in Table 2. The impedance spectra of the perovskite
generally show two arcs. The high-frequency arc is linked to
bulk recombination, while the low-frequency arc represents
interfacial interactions.44,45 The intercept point, in the Nyquist
ACS Appl. Energy Mater. XXXX, XXX, XXX−XXX
ACS Applied Energy Materials
Figure 11. Nyquist plots of PSCs with no additive and with DMSO
and DBEA taken at 80% of Voc. The equivalent circuit used to fit these
curves is shown as an inset.
Table 2. Electrochemical Impedance Parameters of PSCs
with and without Additives (DBEA and DMSO) Extracted
from Fitted Curves Using a Standard Equivalent Circuit
Shown in Figure 11
additive R1 (ohm) R2 (ohm) R3 (ohm) C1 (μF) τ (ms)
no 45.30 906.1 128.7 0.47 0.06
DMSO 21.9 548.0 174.3 0.65 0.11
DBEA 17.4 103.2 558.6 1.05 0.59
plot, along the real part represents series resistance (Rs) that
mainly stems from the FTO and contact resistance. All devices
show comparable series resistance except for devices that have
no additives. Pristine devices show sluggish transport proper-
ties with the highest charge transfer resistance of 906.1 Ω,
lowest geometric capacitance of 0.47 μF, and lowest
recombination resistance of 128.7 Ω for all the devices.
These parameters result in the lowest carrier lifetime values (τ
= 0.06 ms), which is one of the most important determiners of
PV properties of solar cells. DBEA-incorporated cells, on the
other hand, show the best transport dynamics with the lowest
charge transfer resistance of 103.2 Ω, highest geometric
capacitance of 1.05 μF, and much higher recombination
resistance of 558.6 Ω that lead to the highest electron lifetimes
(τ = 0.59 ms). DMSO-based devices exhibited intermediate
properties.
Carrier lifetime is one of the factors that greatly impact the
performance of a solar cell. Electron lifetimes calculated from
the EIS data (τ = RrecomCgeo) are listed in Table 2. It is clear
from the data that devices made with DBEA show much higher
lifetime values compared to DMSO or no-additive devices. In
fact, the lifetimes of DBEA-incorporated solar cells (τ = 0.59
ms) are about five times higher than those of devices made
with DMSO (τ = 0.11 ms) and an order of magnitude higher
than those of pristine solar cells (τ = 0.06 ms). The greatly
enhanced transport properties of DBEA-incorporated devices
can be linked to their improved film characteristics that include
larger grain sizes and a compact and uniform film with fewer
grain boundaries. These improved electrochemical parameters
of DBEA-incorporated devices are responsible for their
excellent PV performance over pristine or DMSO-modified
solar cells.
For ambient air stability studies, devices with DMSO and
DBEA and without any additive were kept at room
temperature under open laboratory conditions without
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encapsulation and their J−V curves were measured with
time. Figure 12 shows the relative efficiency versus storage
Figure 12. Ambient air stability curves of the devices fabricated using
DMSO and DBEA additives in comparison to the pristine device with
no additive. These unencapsulated solar devices were stored in the
dark under an ambient atmosphere. The relative humidity during
storage was 50−70%.
time plots of these devices. It is clear from this plot that devices
made with DBEA retained 78% of their initial efficiency after
600 h in ambient air, while reference and DMSO-added
devices completely degraded under 350 h. Perovskite materials
derive their stability mainly from the interaction of organic
cations and crystal iodide ions. This cation−iodide interaction
in the CH3NH3PbI3 material is highly prone to water
degradation as water readily intercalates into the CH3NH3PbI3
crystals resulting in PbI2 and methylamine. This is why it is
difficult to deposit high-quality CH3NH3PbI3 layers under
ambient air conditions. Earlier studies have demonstrated that
the stability of CH3NH3PbI3 can be significantly improved by
adding molecules (additives) that can interact strongly with
CH3NH3PbI3 crystals and at the same time limit their exposure
to moisture by insulating and passivating their surface and
grains boundaries due their hydrophobic and hydrophilic
functionalities. The enhanced stability of DBEA-modified
devices can be attributed to their much improved film quality,
higher crystallinity, effective grain boundary passivation, and
enhanced hydrophobicity due to stronger coordination
interactions of amine and hydroxyl groups with lead ions
and A-site vacancies along with stronger hydrogen bonding of
hydroxyl groups with the perovskite lattice iodide. Stronger
interactions of DBEA with the perovskite crystal impart greater
stability to the perovskite crystal and its hydrophobic groups
efficiently insulates surface and grain boundaries and thus
significantly limits the ingress of water/moisture. These effects
significantly improve the ambient air stabilities of these
devices. The EIS study, however, clearly demonstrates that
incorporation of DBEA does not adversely impact its charge
extraction capabilities but instead significantly improves the
charge extraction possibly through the improved film proper-
ties.
Although we did not evaluate the stability of these devices
under continuous illumination, however, we did check the
photostability of these films by directly exposing these films to
1 sun illumination under ambient conditions for 24 h. Their
stability was analyzed by monitoring the disappearance of the
perovskite peak and evolution of the PbI2 peak before and after
light illumination and their XRD spectra are shown in Figures
ACS Appl. Energy Mater. XXXX, XXX, XXX−XXX
ACS Applied Energy Materials
S9 and S10 in the Supporting Information. We can clearly see
that the perovskite in the pristine film got almost fully
converted to the corresponding (001) PbI2 peak. This was
accompanied by a color change from brown to bright yellow
(not shown). This confirms the transformation of
CH3NH3PbI3 to pure PbI2. DBEA-incorporated films on the
other hand showed a very little change in the perovskite peak
intensity, but a small PbI2 peak started to become visible. Even
the PbI2 peak in DBEA-added CH3NH3PbI3 after 24 h
illumination is still smaller than the corresponding PbI2 peak in
the as-deposited pristine film (Figures S9 and S10). This
clearly shows the ability of DBEA to impart high stability to
CH3NH3PbI3 through its stronger interaction with perovskite
crystals and its much improved hydrophobicity (increase of
contact angle of the pristine film from 63 to 94°, Figure 2A,B).
For comparison, we also analyzed the DMSO-deposited films
under the same light exposure conditions (Figures S9 and
S10). The DMSO-deposited film showed an almost same
intensity for both the (110) CH3NH3PbI3 and (001) PbI2
peaks, which shows that DMSO does not provide an effective
barrier to CH3NH3PbI3 degradation under ambient air
conditions. These results clearly demonstrate the effectiveness
of DBEA as a stability enhancing agent for CH3NH3PbI3 under
ambient air conditions.
■ CONCLUSIONS
In summary, we have demonstrated the impact of a small
amount of DBEA on the crystallization, film morphology, and
optoelectronic properties of CH3NH3PbI3 films under ambient
air deposition conditions. DBEA through its strong inter-
actions with PbI2 both in solution and during solvent
evaporation significantly reduces the crystallization process,
which leads to highly uniform films. During heating, DBEA-
incorporated films can be converted to uniform, compact, and
highly crystalline perovskite layers with grain sizes over 5 μm.
We have shown that these high-quality films exhibit much
improved optoelectronic properties and deliver a high PV
performance due to effective passivation of the surface and
grain boundaries of CH3NH3PbI3 films by DBEA. The
enhanced hydrophobicity imparted by DBEA helps in
insulating perovskites against unwanted water ingress, which
significantly enhanced the ambient air stability of these
materials in both ambient air and under light illumination.
■
*
ASSOCIATED CONTENT
sı Supporting Information
The Supporting Information is available free of charge at
https://pubs.acs.org/doi/10.1021/acsaem.0c02986.
Elemental analysis of PbI2 films deposited using spin-
coating techniques, effect of different additives on the
grain size of perovskite films, XRD analysis, particle size
distribution analysis, SEM images of the surface
morphology of perovskite crystals at various DBEA
concentrations, FTIR spectra of pristine- and DBEA-
assisted perovskite crystals, J−V curves of the PSCs at
various DBEA concentrations, PV parameters of differ-
ent concentrations of DBEA, J−V parameters of all ten
PSCs fabricated with and without DBEA and DMSO,
and Nyquist plots of PSCs (PDF)
K https://doi.org/10.1021/acsaem.0c02986
■
www.acsaem.org Article
AUTHOR INFORMATION
Corresponding Author
Habib ur Rehman − Department of Chemistry and Chemical
Engineering, School of Science and Engineering, Lahore
University of Management Sciences, Lahore 54792, Pakistan;
Email: habib.rehman@lums.edu.pk
Authors
Mira T. Z. Butt − Department of Chemistry and Chemical
Engineering, School of Science and Engineering, Lahore
University of Management Sciences, Lahore 54792, Pakistan;
School of Engineering and Materials Science and Materials
Research Institute, Queen Mary, University of London,
London E1 4NS, United Kingdom
Syed Zajif Hussain − Department of Chemistry and Chemical
Engineering, School of Science and Engineering, Lahore
University of Management Sciences, Lahore 54792, Pakistan
Xuan Li − School of Engineering and Materials Science and
Materials Research Institute, Queen Mary, University of
London, London E1 4NS, United Kingdom
Joe Briscoe − School of Engineering and Materials Science and
Materials Research Institute, Queen Mary, University of
London, London E1 4NS, United Kingdom; orcid.org/
0000-0002-5925-860X
Complete contact information is available at:
https://pubs.acs.org/10.1021/acsaem.0c02986
Author Contributions
The manuscript was written through contributions of all
authors. All authors have given approval to the final version of
the manuscript. M.T.Z. fabricated and characterized these
devices and wrote this manuscript. S.Z.H. contributed to
analyzing and characterizing the perovskite films along with
drawing the schematics of perovskite fabrication and
mechanism. X.L. helped in characterizing these devices. J.B.
cosupervised the project in QMUL and proofread the
manuscript. H.u.R. conceived the idea, supervised the work,
and helped in writing and editing the manuscript.
Notes
The authors declare no competing financial interest.
■
ACKNOWLEDGMENTS
We are thankful to HEC Pakistan for its support through its
grant number 3586 supported under the NRPU program and
LUMS through the Faculty Initiative Fund (FIF) grant.
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