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Cite this: J. Mater. Chem. A, 2014, 2,

18742
Received 25th August 2014
Accepted 24th September 2014

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High performance perovskite solar cells by hybrid

chemical vapor deposition
Matthew R. Leyden, Luis K. Ono, Sonia R. Raga, Yuichi Kato, Shenghao Wang
and Yabing Qi*

DOI: 10.1039/c4ta04385e
www.rsc.org/MaterialsA

Organometal halide based perovskites are promising materials for

solar cell applications and are rapidly developing with current devices
reaching
19% eciency. In this work we introduce a new method of
perovskite synthesis by hybrid chemical vapor deposition (HCVD), and
demonstrate eciencies as high as 11.8%. These cells were found to
be stable with time, and retained almost the same eciency after
approximately 1100 h storage in dry N2 gas. This method is particularly
attractive because of its ability to scale up to industrial levels and the
ability to precisely control gas ow rate, temperature, and pressure
with high reproducibility. This is the rst demonstration of a perovskite

been previously synthesized by CVD,12,13 but this work is the rst

to use CVD to demonstrate any solar cell eciency. The reported stability of perovskite lms can vary signicantly. In one
case, perovskite is reported to decay substantially to 20% of its
original performance over the course of 6 days in a N2 environment,6 and in others it is reported to be stable for 500 h in air
without encapsulation.14
Perovskite solar cells made by HCVD were shown to be stable
up to 1100 h in a N2 environment, which warrants further study
of stability under ambient conditions.

solar cell using chemical vapor deposition and there is likely still room
for signicant optimization in eciency.

Results and discussion

Introduction
Organometal halide perovskite based solar cells have been
rapidly improving in recent years. In 2009 eciencies were
around 4%,1 but in 5 years time that number has more than
quadrupled to
19%.26 Due to perovskite's broad spectral
absorbance, low temperature processing, and low cost of
materials it is a promising material for low cost solar cells. To
achieve easier fabrication and better reproducibility, we used a
two-step method of perovskite synthesis where a layer of metal
halide (e.g. PbCl2 and PbI2) is deposited, followed by the addition of an ammonium halide salt (e.g. methyl ammonium
iodide, formamidinium bromide). In this method, a solid
powder is converted to the gas phase in a dedicated zone of the
tube furnace and then deposited onto substrates downstream in
another zone of the tube furnace. Because of the use of solid
precursors, this method can be viewed as a form of hybrid
chemical vapor deposition (HCVD). Two-step processes where
methyl ammonium halide is deposited by spin coating or vapor
phase can reach eciency as high as 15%.711 Perovskite has
Energy Materials and Surface Sciences Unit, Okinawa Institute of Science and
Technology Graduate University, 1919-1 Tancha, Onna-son, Okinawa, 904-0495,
Japan. E-mail: yabing.qi@oist.jp
Electronic supplementary
10.1039/c4ta04385e

information

(ESI)

18742 | J. Mater. Chem. A, 2014, 2, 1874218745

available.

See

DOI:

Multi-zone HCVD has independent precise control of pressure,

gas ow rate, methyl ammonium iodide (MAI) temperature, and
substrate temperature, which helps improve reproducibility
and performance. For example, by controlling the pressure (1 Pa
to 1 atm), the diusion rate (Dg f T3/2/P, where Dg is the gas
diusion constant, T is the temperature, and P is the pressure)15
can be varied over a wide range, which is expected to provide
more exibility in controlling the lm growth and possibly will
lead to higher performance. The easy but rigorous process
control and capacity to fabricate large uniform lms is also
expected to facilitate scale-up. In this work, perovskite is fabricated by a two-step method where lead chloride is rst deposited onto appropriate substrates by thermal evaporation in high
vacuum, followed by vapor phase deposition of MAI using
HCVD. Lead chloride is used because it was observed to produce
a more uniform lm by evaporation than PbI2, and is reported
to increase the charge diusion length in perovskite lms.16,17 It
is expected that other metal halide precursors prepared by
vacuum evaporation or solution processing are also compatible
with our HCVD method. For example, a solution based method
of PbI2 deposition was used with HCVD and it demonstrated
some eciency. Fig. 1a shows an example of the HCVD deposition process, in which PbCl2 and MAI are used. The substrates
(uorine doped tin oxide (FTO) glass substrate/TiO2 compact
layer pre-deposited with PbCl2) and MAI are loaded into two

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Fig. 1 Hybrid chemical vapor deposition based perovskite synthesis (a)

diagram of the HCVD furnace and MAI deposition onto metal halide
seeded substrates. (b) Layered structure of a complete solar cell
fabricated by a HCVD process. The complete solar cell is a glass
substrate followed by a FTO layer, an electron transport layer, a
perovskite layer, a hole transport layer, and a top metal contact.

separate temperature control zones of the furnace. The furnace

is then sealed, pumped down to a certain pressure and purged
with inert gas. The diusion of MAI takes place in two phases.
First the MAI must diuse to the substrate in the gas phase
(Dg f T3/2/P). Once the MAI has landed onto the substrate it
must diuse through the lm (i.e., solid diusion) to react with
the metal halide present at the bottom surface. In the case of
solid diusion, the diusion constant is determined by the
Arrhenius equation (Ds f eC/kT, where Ds is the gas diusion
constant, C is a constant, k is Boltzmann's constant).18 Higher
temperatures will increase both gas and solid diusion rates,
and increase the speed of perovskite conversion.
A schematic diagram of a complete solar cell and the layers
within is shown in Fig. 1b. The electron transport layer (ETL) of
the cell is FTO coated with a thin lm of titanium oxide made by
spray pyrolysis. This is followed by the deposition of a metal
halide layer and HCVD perovskite synthesis. The hole transport
layer (HTL) is a lm of spiro-MeOTAD spun onto the perovskite
surface followed by gold top electrode deposition via evaporation. A photograph of a complete, functioning device is shown

Journal of Materials Chemistry A

in Fig. 2a. From this image, we can see that the lm is partially
transparent and homogeneous. The absorbance spectrum was
taken on a complete device (Fig. 2b) and the absorption edge
was measured to be at 781 nm (ref. 14) making it suitable for
applications like photovoltaic windows and multi-junction solar
cells.19
The furnace zone with MAI was heated to 185  C, and the
zone with the substrate was heated to a nominal temperature of
130  C. Due to the ow of hot gas, the temperature inside the
growth region is a gradient between the two set temperatures.
Specically, substrates were usually loaded in the region that
reaches a maximum temperature between 160  C and 170  C.
Samples that were placed in a region hotter than 170  C were
not observed to correctly form perovskite. The initial PbCl2 layer
was converted into a yellow lm of PbI2 in the high temperature
regions of the furnace (ESI, Fig. S1). This suggests that the
substrate temperature was too high, and that there is a
maximum temperature of perovskite formation around 170  C.
Substrates that were loaded in zones with a maximum
temperature of 145  C were found to be unstable. Perovskite
formed at this temperature rapidly turned transparent when
exposed to air. Independent control of temperature zones and
control of pressure provide signicant advantages over existing
vapor deposition methods.9 The additional degree of control
may open the door for fabrication of a wider range of perovskite
materials.
Thermal evaporation was used to deposit the metal halide
layer because it oers good uniformity and thickness control. The
resulting perovskite lms show a relatively smooth morphology
with complete coverage (RMS roughness 28  10 nm, on

Analysis of perovskite lms. (a and b) Atomic force microscopy

3D images of the perovskite thin lm on the silicon substrate in true
proportion. The silicon substrate was prepared under the same
conditions and at the same time as those used for the highest performing device. (a) 40  40 mm2 scan of a perovskite lm with 18 nm
RMS roughness. (b) 2  2 mm2 image showing the laminate structure of
the perovskite grains. (c) X-ray diraction spectrum of the working
perovskite solar cell. The major perovskite peaks (110) at 14.1 , and
(220) at 28.4 are clearly shown.
Fig. 3

Transmission through the complete perovskite solar cell. (a)

Back view of the complete HCVD solar cell with front illumination from
a uorescent light bulb; (b) UV-vis spectrum of a complete cell
showing an absorption edge at 781 nm.

Fig. 2

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Journal of Materials Chemistry A

silicon). Fig. 3a and b show AFM images of perovskite lms in

true proportions (i.e., the lengths along the lateral and vertical
directions have the same scale). This surface roughness is similar
to the roughness of the FTO/TiO2 substrates used for solar cells
(
27 nm). A perovskite lm on the FTO/TiO2 substrate was
measured to have a roughness of
50 nm. In contrast, solar cells
that are fabricated by a solution process oen leads to incomplete coverage, and consequently a much higher roughness.20
Having lower surface roughness allows for thinner lms on top of
the perovskite, such as the hole transport layer and metal contact
layer, which likely will lead to better optimized devices. Also in
this work, the two top lms correspond to the most expensive
materials used, and having thinner lms may help reduce
manufacturing cost. The grains of perovskite lms prepared by
HCVD are typically between 0.2 and 2 mm in size, with an average
size of approximately 0.6  0.4 mm.
It appears that PbCl2 is mostly converted to perovskite
during the CVD process. Film thicknesses are measured before
and aer the CVD deposition process and it is found to increase
by a factor of 3.0  0.2. It is possible to make an estimate of the
thickness increase of fully converted perovskite assuming
densities of lead chloride and perovskite to be 5.85 g cm3 and
4.17 g cm3, respectively.21 With these assumed densities, the
expected volume would increase by a factor of 3.1, which is in
good agreement with measured values and indicates that the
perovskite is fully converted. Fig. 3c shows the X-ray diraction
(XRD) spectrum of the perovskite lm and the observed characteristic diraction peaks at 14 and 28.4 correspond to the
(110) and (220) planes. The spectrum also reveals the presence
of other orientations: (112) at 20.0 , (211) at 23.5 , (202) at 24.5 ,
(312) at 32.0 , (224) at 40.6, and (314) at 43.2 .22 There are also
peaks associated with the substrate, which are predominately
due to SnO and are found at 26.5 , 33.7 , 37.9 , and 51.5 . The
relatively high intensity of peaks at orientations other than (110)
and (220) suggests that perovskite lms grown by HCVD are not
highly oriented with respect to the substrate, which appears
consistent with the AFM image in Fig. 3a. For some perovskite
samples, X-ray diraction spectra reveal a peak at 12.6 associated with the presence of PbI2. If present, these peaks are
generally smaller compared to the main (110) perovskite peak,
indicating that the resulting lm mainly consists of perovskite.
One of the most important parameters observed is the
thickness of the pre-deposited PbCl2 layer and subsequent
perovskite. The average performance of solar cells with dierent
PbCl2 layer thicknesses is shown in Fig. 4a. There appears to be
a peak in eciency at PbCl2 layer thickness approximately 100
nm, or approximately 300 nm of perovskite. It has recently been
proposed that lower open-circuit voltage (Voc) and ll factor (FF)
observed for solar cell devices with a perovskite lm thickness
in excess of 300 nm can be due to the low hole mobilities of the
electron blocking layer.23 Alternatively, poor performance with
thick lms may be due to perovskite grains smaller than the
thickness of the lm.24 This trend is most clearly observed when
considering the ll factor as a function of thickness (ESI,
Fig. S2). Furthermore, it was found that post annealing
substrates in air rather than in N2 signicantly improves Voc,
short-circuit current density (Jsc), and FF. The surface

18744 | J. Mater. Chem. A, 2014, 2, 1874218745

Communication

Perovskite solar cell performance. (a) Eciency as a function of

lm thickness. Scatter plot of average eciencies of solar cells at
dierent seed layer thicknesses. Black dots represent cells that were
annealed in N2 and the red diamonds represent cells that were
annealed in air. (b) IV measurements on the top performing batch of
solar cells. The cells have
300 nm of perovskite grown by HCVD. The
curves shown were measured
500 h after device fabrication.
Fig. 4

morphology aer air annealing was observed to be dierent

than surfaces annealed in a N2 environment. It is very likely that
the eect we observe in this work is similar to the solvent
annealing eects as reported recently by Xiao et al.24 A set of air
annealed solar cells, including the best performing cell
demonstrated, is shown in Fig. 4b. This batch of solar cells had
an average measured PbCl2 thickness of 103  3 nm and an
average measured perovskite thickness of 296  4 nm. The
devices from this batch annealed in N2 had an average eciency
of 6.1% and a maximum of 8.8%, while the devices annealed in
air had an average eciency of 10.8%, and a maximum of
11.8%.
To monitor the stability of perovskite solar cells made by
HCVD, some samples were measured aer 4501100 h of storage
in a N2 glove box. On average, the cells maintained their eciency (ESI, Fig. S3). For example, the highest performing
sample was measured about 1100 h aer the initial measurement
and was found to have similar eciency to the original
measurement. Aer 1100 h, the cell's Voc decreased slightly
(1%) but Jsc (+2%) and FF (+5%) increased. The solar cell
performance measurements were performed in ambient air with
a temperature of
25  C and a relative humidity of
50%.
Between the measurements, the samples were stored in the dark,
inside a N2 glove box with H2O and O2 levels less than 0.1 ppm.
The cell has spent a total of approximately 8 h outside of the N2
glove box for measurements. The stability observed in our solar
cells is likely related to the fact that perovskite in our HCVD
method reaches temperatures above 160  C. At a temperature
above 160  C, excess MAI and incorporated water are expected to
evaporate completely. The HCVD process forms perovskite with a
constant ow of MAI and may be prone to absorb excess MAI. A
lm of MAI is hygroscopic and will likely cause instability issues.
Thermogravimetric analysis shows that a MAI powder sample
starts to lose mass at 145  C (ESI, Fig. S4). This is consistent with
the observation that the minimum temperature of stable perovskite formation is higher than 145  C.
Similar to perovskite solar cells that are fabricated with other
methods, devices fabricated by HCVD suer from hysteresis.22

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The top performing cell showed substantially lower (7.0%)

eciency when measured in the reverse bias (ESI, Fig. S5).
Further optimization of parameters such as layer thickness,
MAI deposition temperature and time, and annealing conditions could yield performance similar to those of the highest
performing solar cells, but is beyond the scope of this study.

Experimental
Details involving synthesis, fabrication and measurement are
included in the ESI.

Conclusions
To summarize, we developed a new method of perovskite
synthesis by hybrid chemical vapor deposition (HCVD). The
solar cells fabricated by this method not only achieved eciencies as high as 11.8%, but also exhibited decent stability
showing almost the same eciency aer approximately 1100 h
storage in dry N2 gas. HCVD is of particular advantage due to its
ability to scale up to industrial levels and the ability to precisely
control gas ow rate, temperature, and pressure with high
reproducibility. It is expected that process optimization of
HCVD can further improve performance.

Acknowledgements
The authors would like to acknowledge the nancial support
from the Okinawa Institute of Science and Technology Graduate
University in Japan.

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