You are on page 1of 12

Nanoscale

View Article Online

Published on 30 June 2014. Downloaded by Sungkyunkwan University on 04/11/2014 09:00:11.

PAPER

View Journal | View Issue

Cite this: Nanoscale, 2014, 6, 9127

Controlling the surface nanostructure of ZnO and


Al-doped ZnO thin lms using electrostatic
spraying for their application in 12% ecient
perovskite solar cells
Khalid Mahmood,* Bhabani Sankar Swain and Hyun Suk Jung*
In this paper, ZnO and Al-doped ZnO lms were deposited using the electrospraying method and studied
for the rst time as photoanodes for ecient perovskite solar cells. Eects of substrate temperature,
deposition time, applied voltage, substrate-to-nozzle distance and ow rate (droplet size) on the
morphology of ZnO were studied with the help of FE-SEM images. The major factors such as the droplet
size of the spray, substrate temperature and substrate-to-nozzle distance at deposition control the lm
morphology. Indeed, these factors determine the density of the lm, its smoothness and the ow of
solution over the substrate. The droplet size was controlled by the ow rate of the spray. The substrateto-nozzle distance and ow rate will both regulate the solution amount deposited on the surface of the
substrate. The most favorable conditions for a good quality ZnO thin lm were a long substrate-tonozzle distance and lower solution ow rates. In situ droplet size measurement shows that the size and
dispersion of particles were narrowed. The method was shown to have a high deposition rate and
eciency relative to well-established thin lm deposition techniques such as chemical and physical
vapor deposition. In addition, it also allows easy control of the microstructure and stoichiometry of the
deposits. The pure ZnO lm produced under optimum conditions (440 nm thick) demonstrated a high
power conversion eciency (PCE) of 10.8% when used as a photoanode for perovskite solar cells, owing
to its high porosity, uniform morphology and ecient electron transport. For thicker lms a drastic
decrease in PCE was observed due to their low porosity. We also observed that the open-circuit voltage

Received 16th April 2014


Accepted 15th May 2014

increases from 1010 mV to 1045 mV and also the PCE increases from 10.8% to 12.0% when pure ZnO

DOI: 10.1039/c4nr02065k

the reasonably uniform-sized droplets of smaller size, so the lms have a smooth surface and are highly

www.rsc.org/nanoscale

suited for optoelectronic applications.

lms were doped with aluminum (Al). Under atmospheric pressure, the electrospraying system produces

1. Introduction
Electrospraying has gained interest recently for the preparation
of thin lms13 and polymer coatings,4,5 which were logically
combined in electrospray studies for lms and coatings
prepared using polymers.613 Thin lms of ZnO deposited by
electrospraying are homogeneous and dense which enable
them to be used in numerous applications such as biosensors,14
UV-luminescent devices,15 solar cells,1618 and transparent
conductive oxide (TCO) electrodes.1922 One major advantage of
the electrospraying method is that thin lms with nano-/
microscaled structures could be deposited. Moreover, the
morphologies of the lms are easily controlled by changing the
School of Advanced Materials Science & Engineering, Sungkyunkwan University,
Suwon 440-746, Republic of Korea. E-mail: khalid@kaist.ac.kr; hsjung1@skku.edu;
Fax: +82-31-290-7410; Tel: +82-31-290-7403
Electronic supplementary
10.1039/c4nr02065k

information

(ESI)

This journal is The Royal Society of Chemistry 2014

available.

See

DOI:

deposition conditions such as (e.g.: solution properties, droplet


size and applied voltage) and the thickness of the lms can be
adjusted by controlling the deposition time.
The morphology of ZnO lms depends directly on the
particle size and the mode of spreading the solution on the
substrate during the electrostatic spraying process. Smaller
spray droplets will result in smaller particles and smoother
lms. So, precise control of the interplay between droplet size
(ow rate), substrate temperature and particle size is, therefore,
the key to control the lm morphology. Various methods such
as metal organic chemical vapor deposition (MOCVD), spray
pyrolysis, pulse laser deposition and solgel have been used to
control the morphology of ZnO thin lms.2326 It is very dicult
to deal with process parameters for controlling the morphology
of lms in the above mentioned methods. Electrospraying is a
very promising method for the preparation of continuous lms
with controlled morphology at lower temperatures by the suitable adjustment of process parameters. In a recently reported

Nanoscale, 2014, 6, 91279138 | 9127

View Article Online

Published on 30 June 2014. Downloaded by Sungkyunkwan University on 04/11/2014 09:00:11.

Nanoscale

study, we studied the performance of boron and tantalumdoped ZnO thin lms and also investigated the eect of thermal
treatment and dopant concentration on the performance
(electrical and optical properties) of ZnO thin lms.27 In fact,
thermal annealing and dopant concentrations have a signicant eect on the morphology of these lms, which will further
inuence the performance of thin lm based devices Therefore,
the surface morphology of lms is an important factor that can
aect the performance of lm based devices. In this perspective,
the present work is focused on controlling the surface nanostructure using the electrospraying method as a function of
process parameters like the substrate temperature, applied
voltage, the ow rate (droplet size) of the precursor solution,
spraying time and nozzle-to-substrate distance.
Recently, solid state perovskite (CH3NH3PbI3) solar cells
have drawn great attention from researchers owing to their
great benets like ease of fabrication, high eciencies and
cheaper technology.2830 The solid-state solar cells composed of
CH3NH3PbI3 layers fabricated over the mesoporous TiO2 lm
exhibited a high power conversion eciency (PCE) of 9.7% and
also showed good stability for a long time.31 In addition, it was
also demonstrated that in the absence of mesoporous TiO2
layers perovskite solar cells showed a high PCE of 10.9% by
depositing the CH3NH3PbI2Cl layer onto the Al2O3 surface.32
The most recent research development in the area of perovskite
solar cells has shown that the cell eciency can even reach
15%,33 along with a proposed PCE of 20% to be achieved in the
near future, which proves that these cells have great potential to
be commercialized soon.
Two basic approaches have been used to enhance the functionality and the performance of perovskite solar cells. One
solution is to utilize a non-electron-injecting meso-superstructure planar layer and another way is based on an electrontransfer nanostructured oxide layer. In the case of electroninjecting oxide nanostructure lms, mostly mesoscopic TiO2
has been used, needing higher processing temperatures to
enhance the charge transport. In addition to the TiO2 nanoparticle lms used as the electron-injecting layers in perovskite
solar cells, the one-dimensional (1-D) TiO2 and ZnO nanorods
were also studied.30,3438 The ZnO nanostructures also possess
numerous advantages over TiO2 owing to their excellent electron mobility and same band structure as TiO2.39 Furthermore,
n-type characteristics like the conductivity of pure ZnO lms
can be enhanced using metal doping which is also benecial for
shiing the Fermi level (EF) in the direction of the conduction
band (EC).40 Usually, group-III elements such as In, Ga, B and Al
are highly preferable as n-type dopants for ZnO lms. Al-doped
ZnO and Ga-doped ZnO lms are excellent candidates for TCO
materials because they are easy to handle, less toxic, have
suitable ionic radii, are inexpensive and show excellent optical
transmission performance. Especially, for Al-doped ZnO nanostructures it has been proven that Al doping can greatly enhance
the carrier concentration and optical transmittance of pure ZnO
to achieve superior conductivity.41
The properties of ZnO nanoparticulate lms also depend
mainly on the deposition techniques and their microstructures,
which will nally play an important role in reducing the

9128 | Nanoscale, 2014, 6, 91279138

Paper

structural and electronic defects in the lms. Therefore, the


development of a ZnO lm with a low temperature processed
nanoporous structure will be very helpful to produce a lower
concentration of defects and ecient interactions with the solid
sensitizer. In order to achieve ZnO lms with these characteristics, various methods such as chemical bath deposition
(CBD)36 and hydrothermal methods37,38 have been investigated
to grow 1-D ZnO nanorod arrays for their application in the
perovskite solar cells. In addition, other lm deposition
methods such as plasma-enhanced chemical vapor deposition
(PECVD)39 and spin coating42 have also been used to fabricate
thin lms of ZnO as electron-injecting layers for use in perovskite solar cells. Although, these methods have shown a great
capability to deposit ZnO nanostructures to obtain ecient
perovskite solar cells, an alternative spray-coating method such
as electrostatic spraying is also needed which can control the
nanostructure of the ZnO lms in an easier and ecient
manner for further enhancement of PCE of these cells. The key
advantages of the electrostatic spraying method are mentioned
above in comparison with other methods. So far, electrostatic
spray deposited ZnO and Al-doped lms have not been investigated for application in solid state perovskite solar cells.
The present report mainly focuses on the deposition of crack
free ZnO and Al-doped lms as a function of various system
parameters by utilizing electrospraying and they are studied as
electron-transfer layers for perovskite solar cells in order to
enhance the cell performance and develop a cost-eective
alternative electron-transfer layer fabrication method. The
morphology of the lms has been analyzed using eld emission
scanning electron microscopy. The pure ZnO lm produced
under optimum conditions with a thickness of 440 nm gave a
high PCE of 10.8%. For Al-doped lms a higher PCE of 12.0%
was observed due to an increase in open-circuit voltage. To the
best of our knowledge this is the rst study which utilizes the
electrospray deposited mesoporous ZnO and Al-doped lms as
photoanodes to obtain highly ecient perovskite solar cells.

2.

Experimental

2.1. Deposition of mesoporous pure and Al-doped ZnO thin


lms
ZnO and Al-doped ZnO thin lms were deposited using the
electrospraying method as shown in Fig. 1. The spraying solution was prepared using 0.05 M zinc acetate dihydrate in an
ethanolwater (30 : 70 v/v) mixture. Al doping can be achieved
by adding an Al dopant in the form of aluminum chloride (0.5
at.%) into the precursor solution. A syringe pump (KD200, KD
Scientic Inc., USA) was used to transfer the precursor solution
to a small stainless steel nozzle. The precursor solution ow rate
ranges from 0.001 mL min1 to 0.007 mL min1. The high
voltage (0 to 7 kV) was varied between the needle tip and the hot
plate, using a dc power supply (Korea switching, Inc., Korea).
The distance between the needle tip and the substrate was
varied between 1 cm and 4 cm. Fluorine-doped tin oxide (FTO)
substrates were washed with isopropyl alcohol (IPA), ethanol,
acetone and water for proper cleaning. The deposition time
ranged from 40 to 120 minutes and the temperature of the

This journal is The Royal Society of Chemistry 2014

View Article Online

Published on 30 June 2014. Downloaded by Sungkyunkwan University on 04/11/2014 09:00:11.

Paper

Fig. 1

Nanoscale

Schematic illustration of the electrostatic spraying deposition setup.

heating plate ranged from 100 to 170  C. A conventional digital


camera (model no. 7309P-1) assembled with a lens and a light
source was used to capture the spray patterns.

dissolved in 1 mL chlorobenzene) solution for 30 s at 3000 rpm.


Finally, approximately a 90 nm thick Ag lm was deposited using
thermal evaporation over this layer.

2.2. Fabrication of CH3NH3PbI3 perovskite solar cells

2.3. Characterization

Perovskite solar cells were prepared using the sequential deposition method as reported elsewhere.28 Firstly, a very thin
compact layer of ZnO or Al-doped ZnO named the blocking layer
was deposited onto FTO substrates by spin coating the above
mentioned precursor solution at 4000 rpm for 30 s and annealed
in air at 350  C for 30 minutes. Then 1 M PbI2 solution was made
in DMF while stirring overnight, at a constant temperature of
70  C. The as-deposited photoelectrodes contained ZnO and Aldoped ZnO thin lms were spin coated at 6000 rpm for 5 s, using
the above solution. Then the PbI2 coating was allowed to dry for
30 minutes at 70  C. Aerwards, the lms were dipped into a 10
mg mL1 solution of CH3NH3I in IPA for about 20 minutes, followed by rinsing in IPA and drying at 70  C for 30 minutes. The
hole transporting layer was made by spin coating the spiroOMeTAD Hole (80 mg of 2,20 ,7,70 -tetrakis(N,N-di-p-methoxyphenyl-amine)-9,90 -spirobiuorene, 8.4 mL of 4-tert-butylpyridine,
and 51.6 mL of bis(triuoromethane) sulfonamide lithium salt
(Li-TFSI) solution (154 mg mL1 in acetonitrile), all mixtures were

Cross-sectional and surface morphologies were obtained using


scanning electron microscopy (SEM, JSM-7600F, JEOL). The
elemental composition of doped lms was conrmed using
energy dispersive X-ray spectra (EDS; DX-4). The crystallinity of
lms was checked using an X-ray diractometer (XRD; model
M18XHF, Macscience Instruments). X-ray photoelectron spectra
(XPS) were used to check the purity and composition of lms
using X-ray photoelectron spectroscopy (Thermo VG Scientic,
Sigma Probe). The optical transmittance spectra were obtained
using a UV-visible spectrometer (UV-3101PC). Photovoltaic
properties were measured by using a potentiostat (CHI660, CHI
instrument). The solar spectrum under AM 1.5 conditions was
simulated with a solar simulator (Oriel Sol 3A class AAA, Newport) to measure the current voltage characteristics. The incident photon to current conversion eciency was measured with
an IPCE measurement system (PV Measurements). A phase
Doppler particle analyzer (PDPA, TSI., USA) was used to observe
the size distribution of sprayed droplets.

This journal is The Royal Society of Chemistry 2014

Nanoscale, 2014, 6, 91279138 | 9129

View Article Online

Nanoscale

3.

Results and discussion

Published on 30 June 2014. Downloaded by Sungkyunkwan University on 04/11/2014 09:00:11.

3.1. Size distribution of sprayed droplets


Fig. S1a exhibits the size distribution of droplets in real time.
By controlling the solution ow rate, the diameter of sprayed
droplets was adjusted accordingly. The diameter of droplets
increased as the ow rate increased under a constant applied
voltage (5.9 to 6 kV). Geometric standard deviation (GSD) was
used to identify and describe the sprayed droplets' uniformity.
The GSD and geometric mean diameter (GMD) as a function
of dierent ow rates are exhibited in Fig. S1b and c, respectively. GSD values range from 1.39 to 1.47, which describe the
uniform-sized droplets, and the GMD values change from 2.73
to 2.94 mm for all ow rates.
Since the electrospraying technique generates droplets of
uniform size which will result in the formation of better quality
lms with uniform-sized particles.
3.2. Operating envelope for the atomization of solution and
the formation of a charged jet
To control the lm morphology the solution properties in terms
of electrospraying are very crucial to be optimized. Typically, for
the electrospraying technique the understanding of the operating envelope and other system parameters such as the solution ow rate, substrate temperature, applied voltage and
substrate-to-nozzle distance is very important to control the lm
morphology.
Lord Rayleigh rstly explained the development of charged
jets as follows:
1=3  2=3

93g
F
rj
(1)
2p2
I
where F is the solution ow rate, I is the injection current, g is
the surface tension, and 3 is the permittivity of the solution.43
Especially, electrospraying ociates by activation of surface
charges on the sprayed uid with the help of applied
voltage.4447 The generation of a ne spray of solvents with low
dielectric constant (3) might be tough. On the other hand, by
utilization of a sharp nozzle, electrons can be easily injected
into or removed from the uid (led-injection) for generating an
ionized solution with enhanced capacity to transfer the surface
charge in a process called as eld ionization.
To obtain the stable cone-jet mode with monodispersed
electrospray droplet generation, a minimum and maximum
range of ow rate should be adjusted using a specic nozzle
type. The minimum and the maximum ow rates used to obtain
the stable cone-jet mode were 0.001 mL min1 and 0.025 mL
min1 along with the applied voltage, and various modes of
spraying such as dripping, micro-dripping, spindle, unstable
cone-jet, stable cone-jet and the multi-jet modes are exhibited
in Fig. S2. It was observed that at zero voltage and a ow rate of
0.003 mL min1, the dripping mode was obtained. The surface
tension results in the formation of large drops until the droplets' weight becomes too high for the surface tension and
capillary force to dominate. The small increase in voltage from
zero to 3.8 kV micro-causes the dripping mode to appear. At this

9130 | Nanoscale, 2014, 6, 91279138

Paper

stage, more charges were collected at the meniscus surface


providing the intense electric tension forces away from the
nozzle. Consequently, the size of droplets dripping o of the
nozzle decreases and the density of drops increases. When the
applied voltage was further enhanced to 5.5 kV, unstable conejet mode was obtained. Once the electric force was great enough
(6 kV), the charged surface was disturbed into a smooth thin jet,
which nally breaks-up into small (2.8 mm) fairly uniform
sized droplets. This is called as stable cone-jet mode. At a much
higher voltage of about 7 kV multi-jet spray mode was obtained.
3.3. Eect of applied voltage
Rayleigh's equation (eqn (1)) describes that the enhancement of
current (I) present on the precursor solution will decrease the
diameter of the jet. Upon increasing the applied voltage, the
current can be eciently controlled since V is dependent on I,
by keeping other parameters constant.
In order to study the eect of applied voltage on the lm
morphology, the zinc acetate dihydrate precursor solution at a
ow rate of 0.003 mL min1 was deposited on the FTO substrate
with a 4 cm distance at 150  C for 60 min. The applied voltage is
varied from 3.8 kV to 7 kV. Fig. 2 shows clearly that the lm
morphology was inuenced by increasing the applied voltage by
keeping other parameters constant. A continuous and dense
thin lm was obtained only at a high voltage of 6 kV, where the
stable cone-jet mode was observed because the increase of
applied voltage leads to the formation of a thin jet and
reasonably distributed droplets. While at lower voltages, the
larger droplet formation takes place that still contained the
solvent to evaporate upon deposition.
3.4. Eect of substrate temperature
The deposition of lms using the electrospraying technique is
the result of co-action of evaporation of the solvent in the
spraying droplets and salt precipitation in precursor solution as
soon as it reaches over the heated substrate. Therefore, the
temperature of the substrate is a crucial factor since it decides
the precursor decomposition and the rate of solvent
evaporation.
This study also emphasizes the discovery of appropriate
process parameters for the fabrication of uniform and dense
ZnO lms. As mentioned in the Experimental section, the zinc
acetate dihydrate precursor solution has been prepared and
sprayed onto a glass substrate from a distance of 4 cm at a ow
rate of 0.003 mL min1 for 60 min at an applied voltage of 6 kV.
The substrate temperature was varied from 100 to 170  C.
Fig. 3 shows the surface morphologies of ZnO thin lms
deposited at substrate temperatures of 100, 130, 150 and 170  C,
respectively. It was observed that the increase in substrate
temperature has little inuence on the morphology of ZnO
lms. At very low temperature such as 100  C, porous spherical
shaped microstructures can be observed while at the optimal
temperature of 150  C the pores disappeared and the lm is
dense without any cracks. The heat of the substrate inuences
the lm surface and the radiative heat transfer causes the
sprayed droplet temperature to increase before they strike the

This journal is The Royal Society of Chemistry 2014

View Article Online

Published on 30 June 2014. Downloaded by Sungkyunkwan University on 04/11/2014 09:00:11.

Paper

Nanoscale

Inuence of the applied voltage on the morphology of ZnO thin lms deposited on the FTO substrate at a ow rate of 0.003 mL min1
from a distance of 4 cm at 150  C for 60 min: (a) 3.8 kV, (b) 5.5 kV, (c) 6 kV, and (d) 7 kV, respectively.
Fig. 2

surface of the substrate. Therefore, solvent evaporation in the


droplets takes place before they approach the substrate surface
and higher temperature will increase the solvent evaporation

rate. Moreover, the solvent in droplets smaller in size will


evaporate faster before they reach the substrate and eventually
strike over the substrate surface in the form of solid dried

Inuence of substrate temperature on the morphology of ZnO thin lms deposited on the FTO substrate at a ow rate of 0.003 mL min1
from a distance of 4 cm for 60 min and an applied voltage of 6 kV: (a) 100  C, (b) 130  C, (c) 150  C, and (d) 170  C, respectively.
Fig. 3

This journal is The Royal Society of Chemistry 2014

Nanoscale, 2014, 6, 91279138 | 9131

View Article Online

Published on 30 June 2014. Downloaded by Sungkyunkwan University on 04/11/2014 09:00:11.

Nanoscale

particles. Furthermore, when the substrate temperature was


between 100  C and 130  C, pores appeared over the lm surface
revealing intense contraction during the lm formation
process. Indeed, while spraying is in process, some quantity of
the solution gets to the surface of the substrate and a thin layer
of liquid was formed on the top. As the spraying is completed
the temperature of the thin liquid layer increases sharply which
causes the solvent to evaporate at a faster rate which results in
the stress development in the lm. Thus, the lm deposited at
low temperature was not dense and continuous. Moreover, if
the substrate temperature is increased further, the rate of lm
drying and the degree of damage decreased. The optimized
temperature of about 150  C allows a dense and uniform sized
lm. In addition, the eect of substrate temperature should be
connected with the solution ow rate or the substrate-to-nozzle
distance, since these factors eectively control the solution
quantity reaching the surface of the substrate.
3.5. Eect of precursor solution ow rate
The ow rate of precursor solution decides the amount of liquid
that approaches the surface of the substrate for a specied time.
On the other hand, the droplet size can be controlled by
adjusting the ow rate, expressed by the following equation:48
 1=3
Q
d  3r 1=6
(2)
k
where Q is the precursor solution ow rate, 3r is the relative
solution permittivity and k is the electrical conductivity of the
precursor solution. According to it, the larger the ow rate, the

Paper

larger will be the droplet size which is also conrmed by


Fig. S1a. Moreover, for larger size droplets the solvent will
evaporate slowly during the spraying process. Thus, at higher
ow rates a larger amount of solution will reach the substrate
surface.
To evaluate the eect of ow rate on the lm morphology,
the precursor solution was sprayed onto the FTO substrate
using 4 cm distance at 150  C for 60 min and an applied
voltage of 6 kV. The precursor solution ow rate was varied
from 0.001 mL min1 to 0.007 mL min1. Fig. 4 reveals that
the lm morphology was inuenced by increasing the ow
rate. A continuous and dense thin lm was obtained only at a
low ow rate of 0.003 mL min1. As mentioned before, a
liquid will accumulate over the substrate surface at higher
ow rates. If it gathered over the substrate surface in a
larger amount then cracks and pores will be observed in
the lms because a longer drying period will produce
stress in the lms. Thus, the lm forming at larger ow
rates will contain larger particles and pores as exhibited in
Fig. 4.
3.6. Eect of substrate-to-nozzle distance
Variation in the distance between substrate and nozzle will
modify the transition of matter which approaches the substrate.
Specically, the same amount of solution is sprayed over a
larger substrate area, if the substrate-to-nozzle distance is
increased and vice versa. By keeping in mind the relationship
between the amount of liquid remains on the surface of the
substrate and the quality of lms in terms of morphology as

Fig. 4 Inuence of ow rate on the morphology of ZnO thin lms deposited on the FTO substrate at 150  C from a distance of 4 cm for 60 min
and an applied voltage of 6 kV: (a) 0.001 mL min1, (b) 0.003 mL min1, (c) 0.005 mL min1, and (d) 0.007 mL min1, respectively.

9132 | Nanoscale, 2014, 6, 91279138

This journal is The Royal Society of Chemistry 2014

View Article Online

Published on 30 June 2014. Downloaded by Sungkyunkwan University on 04/11/2014 09:00:11.

Paper

Nanoscale

Fig. 5 Inuence of substrate-to-nozzle distance on the morphology of ZnO thin lms deposited on the FTO substrate at a ow rate of 0.003 mL
min1 at 150  C for 60 min and an applied voltage of 6 kV: (a) 1 cm, (b) 2 cm, (c) 3 cm, and (d) 4 cm, respectively.

discussed previously, a longer distance will yield a better


morphology while a shorter distance produces defects in the
lms.

To investigate the eect of substrate-to-nozzle distance on


lm morphology, the precursor solution was sprayed onto the
FTO substrate at 150  C, at a ow rate of 0.003 mL min1 for 60

Fig. 6 Inuence of deposition time on the morphology of ZnO thin lms deposited on the FTO substrate from a distance of 4 cm at 150  C, at a
ow rate of 0.003 mL min1 and an applied voltage of 6 kV: (a) 60 min, (b) 80 min, (c) 100 min, and (d) 120 min, respectively.

This journal is The Royal Society of Chemistry 2014

Nanoscale, 2014, 6, 91279138 | 9133

View Article Online

Published on 30 June 2014. Downloaded by Sungkyunkwan University on 04/11/2014 09:00:11.

Nanoscale

Paper

min and an applied voltage of 6 kV. In addition, the substrateto-nozzle distance was altered from 1 to 4 cm. The microstructural changes are shown in Fig. 5, agreed well with our
assumption: the lm formation using short distances is not
continuous and particles are not uniform in size and the
intermediate one also shows a porous structure, while the
longer distance of 4 cm produces a dense and uniformly sized
lm.
It is remarkable that a longer substrate-to-nozzle distance is
complement to the lower ow rates. Because, most of the
solvent evaporates during the ight of droplets from the nozzle
to the surface of the substrate as shown in Fig. 5. Furthermore,
it also decreases the quantity of solution reaching over the
surface of the substrate in the same way as the decrease of ow
rate eects.
3.7. Eect of deposition time
In order to inquire the eect of deposition time on the lm
morphology, the zinc acetate dihydrate solution was sprayed on
the FTO substrate with 4 cm distance at 150  C, at a ow rate of
0.003 mL min1 and an applied voltage of 6 kV. The deposition
time has been varied from 60 to 120 minutes.
Fig. 6 shows the FESEM images of ZnO thin lms as a
function of deposition time. With the increase of deposition
time from 60 to 120 minutes the particle size increased. From a
previous report by Chen and co-workers,49 the formation of a
dense lm was clear evidence that the solvent in the droplets
has not been totally evaporated, when it approached the surface
of the substrate. Moreover, the droplet liquid might spread on
the surface of the substrate and form a continuous layer. At
deposition temperatures, where the incoming sprayed droplets
are still wet but provide adequately high decomposition and
evaporation rates, the dispersion of sprayed droplets on the
surface of the substrate will form a continuous layer. By
increasing the deposition time, the spreading of sprayed droplets will occur on the surface of the layer made which has a
surface tension dierent from that of the substrate. In addition,
the solution wettability on the deposited layer is less than that
on the substrate. Thus, by keeping the substrate temperature
constant, the increase of deposition time will lead to slower
spreading of sprayed droplets and individual particles might be
formed that can increase the surface roughness.50 Furthermore,
our results agree well with a previously reported study.51
3.8. Correlation between the electrospraying process
parameters
Aer controlling the surface nanostructure using various
process parameters systematically, a rational image about the
electrospraying technique for preparing a dense and crack free
ZnO lm is developed using the correlation between solution
ow rate, substrate-to-nozzle distances and substrate
temperature.
To obtain better quality ZnO lms, the relationship between
the substrate-to-nozzle distance and the substrate temperature
as a function of dierent ow rates is shown in Fig. 7a. It does
not describe a linear dependency owing to the quadratic

9134 | Nanoscale, 2014, 6, 91279138

Fig. 7 Correlations between the process parameters for optimized


ZnO and AZO thin lms: (a) substrate temperature vs. precursor
solution ow rate for dierent distances; (b) substrate temperature vs.
substrate-to-nozzle distance for dierent ow rates.

relationship between the area covered by the spray and the


substrate-to-nozzle distance. For shorter distances, more
amounts of liquid will reach the surface. Therefore, to evaporate
the solvent completely, a higher temperature is needed. Fig. 7b
exhibits the dependence of substrate temperature on the
precursor solution ow rate as a function of various substrateto-nozzle distances to attain a dense ZnO lm. The trend shows
a linear dependency because a linear relationship exists
between the quantities of solution reaching the substrate and
the ow rate. In the case of higher ow rates, complete evaporation of the solvent can be accomplished using higher
substrate temperatures.
The ow rate and substrate-to-nozzle distance behave in a
similar fashion but in opposite directions since both of them
control the amount of solution that reaches the substrate
surface. The substrate temperature can control the changes in
these two variables to maintain the quality of the lm.
3.9. Solar cell performance for optimized pure and Al-doped
ZnO thin lms
Fig. 8ac show the cross-sectional FE-SEM images of the optimized ZnO lm fabricated at a distance of 4 cm at 150  C, at a
ow rate of 0.003 mL min1 and an applied voltage of 6 kV, with

This journal is The Royal Society of Chemistry 2014

View Article Online

Published on 30 June 2014. Downloaded by Sungkyunkwan University on 04/11/2014 09:00:11.

Paper

Nanoscale

Fig. 8 Cross-sectional FE-SEM images of ZnO thin lms with: (a) 440 nm, (b) 625 nm, and (c) 745 nm thickness, respectively and (d) fabricated
perovskite solar cell with 440 nm thick ZnO lm.

three dierent lm thicknesses of 440 nm, 625 nm and 745 nm


by varying the spraying time of 40, 50 and 60 minutes, respectively. The cross-sectional FE-SEM images show that the ZnO
lms deposited under the optimized conditions with dierent
thicknesses presented a mesoporous structure to achieve both
the optimum charge transport characteristics and better
perovskite loading. Moreover, along with porosity considerations the total thickness of the lm also plays a crucial role in
the cell performance.39 In this regard, a 440 nm thick ZnO thin
lm based perovskite solar cell is shown in Fig. 8d. It is
observed that the pores of the ZnO lm are inltrated with the
absorbance CH3NH3PbI3, and a thin overlayer of CH3NH3PbI3
also exists on the top of the surface covering the ZnO lm
surface. This type of structure is highly suitable for ecient
charge separation and very important for estimating the lling
fraction of the CH3NH3PbI3. The existence of CH3NH3PbI3 as an
overlayer on the top of the ZnO/CH3NH3PbI3 inltrated lm is
very benecial for ecient extraction of charges through the
interface with the hole transporting layer and the top most Ag
layer.39
A comparison of the XRD pattern for pure and Al-doped ZnO
(440 nm thick) lms is exhibited in Fig. S3a. The lms have a
strong (002) peak intensity, indicating that the lms are highly
crystalline in nature, corresponding to a hexagonal wurtzite
structure along the c-axis. Due to the substitution of Al into ZnO
sites, the diraction peaks shied towards the larger or smaller
angle side which conrms the presence of Al doping into the
pure ZnO lms (Fig. S3b). The chemical composition of Aldoped ZnO lms is further conrmed using EDS (Fig. S4). The

This journal is The Royal Society of Chemistry 2014

presence of Al, Zn and O peaks in the EDS spectrum ensures the


presence of Al in the ZnO lm. The substitution of Al into the
ZnO lm is further conrmed through XPS analysis (Fig. S5).
The existence of the Al 2p peak at 73.50 eV in the ZnO lm
revealed that Al is present in the lm (Fig. S5a). Moreover, for
Zn 2p the two peaks corresponding to Zn 2p3/2 and Zn 2p1/2 at
1022.6 and 1045.4 eV (Fig. S5b) demonstrate that Zn atoms are
present in the lm. Furthermore, the scan of the O 1s spectrum
shows a peak around 532.1 eV (Fig. S5c), attributed to the
metal ions which are oxidized in the lm, specically OZn and
OAl in the ZnO lattice. The pure and Al-doped ZnO lms
produced under optimum conditions are highly transparent
(greater than 94%) in the visible region (Fig. S6). The Al-doped
ZnO lm shows slightly higher transmittance compared to the
pure ZnO lms, because the substitution of Al atoms into the
ZnO sites provides an increase in Fermi level in the conduction
band of semiconductors due to enhancement in carriers which
will nally help to widen the optical bandgap. Therefore, a
larger bandgap would increase the optical transmittance in the
visible region.41
The photovoltaic characteristics of dierent ZnO thin lm
thicknesses are shown in Fig. 9a and the detailed photovoltaic
parameters such as short-circuit photocurrent (Jsc), ll factor
(FF) and open-circuit voltage (Voc) are summarized in Table 1.
The optimal thickness of ZnO lms to obtain the enhanced cell
performance is about 440 nm. However, for thicker lms of 625
nm and 745 nm, the Voc reduces from 0.86 V to 0.83 V,
respectively. The decrease of Voc on increasing the lm thickness is attributed to the higher recombination rate caused by

Nanoscale, 2014, 6, 91279138 | 9135

View Article Online

Nanoscale

Paper
Photovoltaic parameters for the perovskite solar cells fabricated with various ZnO lm thicknesses at optimized process
parameters under one sun illumination (AM 1.5G, 100 mW cm2)

Table 1

PCE*a
(%)

ZnO lm
thickness (nm)

Jsc
(mA cm2)

Voc
(mV)

Fill
factor

PCE
(%)

10.8  0.1
4.4  0.2
3.4  0.2

440
625
745

16.0
7.48
5.98

1010
860
830

67.0
69.0
70.0

10.8
4.4
3.4

Published on 30 June 2014. Downloaded by Sungkyunkwan University on 04/11/2014 09:00:11.

PCE* is the power conversion eciency calculated for 6 dierent


devices.

by other researchers for planner ZnO lm based devices,39 and


also for nanober devices.35
The comparison of photovoltaic characteristics of the best
performing 440 nm thick pure and Al-doped ZnO lm based
cells is presented in Fig. 10a and Table 2. The pure ZnO lm
based perovskite cell shows a higher Jsc of 16 mA cm2. On the
other hand, a reduction of Jsc (15.1 mA cm2) is observed for Aldoped ZnO lm based cells. However, the Voc increases from
1010 mV to 1045 mV aer doping with Al which will nally
increase the PCE up to 12%. It is well known that Voc is dened
by the dierence between the n-type semiconductor's quasi

Fig. 9 (a) Photovoltaic performance as a function of pure ZnO lm


thickness and (b) IPCE spectrum for 440 nm thick pure ZnO thin lms.

the higher surface area and as well as the increase of trap


promoting recombination in TiO2 lms.39 On the other hand, a
larger reduction in Jsc values is observed by increasing the ZnO
lm thickness. In fact, the increase of lm thickness will
probably hinder the passage of perovskite inltration into the
ZnO lm which eventually results in a lower loading of perovskite. In addition, thicker lms with irregular shaped particles
and cracks on their surface hindered the ecient electron
transport thus showing a lower PCE. Remarkably, the cells
based on thinner ZnO lms demonstrated the highest PCE of
10.8%, which is much better than that (4.8%) of the cells based
on nanocolumnar plasma deposited ZnO thin lms.39
Incident photon-to-current conversion eciency measurement (IPCE, Fig. 9b) is also performed to further investigate the
ecient electron transportation within the optimized ZnO lm
having a thickness of 440 nm. The eciency of around 80% is
observed along the entire spectrum (370750 nm) which
demonstrates the excellent cell performance. Aer integrating
the product of AM 1.5G photon ux with the IPCE spectrum, the
calculated Jsc is found to be 15.6 mA cm2 which is in good
agreement with measured Jsc values of 16.0 mA cm2 obtained
for a thinner device. The shape of the IPCE spectrum for thinner
ecient devices agreed well with the spectrum shapes reported

9136 | Nanoscale, 2014, 6, 91279138

Fig. 10 Comparison of (a) photovoltaic performance and (b) IPCE


spectra of 440 nm thick pure and Al-doped ZnO thin lms.

This journal is The Royal Society of Chemistry 2014

View Article Online

Paper

Nanoscale

Table 2 Comparison of photovoltaic parameters of the perovskite


solar cells based on 440 nm thick pure and Al-doped ZnO lms

Published on 30 June 2014. Downloaded by Sungkyunkwan University on 04/11/2014 09:00:11.

Film type
PCE*a (%)

Jsc (mA cm2)

Voc (%)

Fill factor (%)

PCE (%)

Pure ZnO lm
10.8  0.1
Al-doped ZnO lm
12.0  0.2

16.0

1010

67.0

10.8

15.1

1045

76.0

12.0

a
PCE* is the power conversion eciency calculated for 6 dierent
devices.

Fermi-level and hole transporting material's (HTM) HOMO level


in nanostructured perovskite solar cells. Thus, the Al-doped
ZnO lm demonstrated the lower recombination rate of the
conduction band electrons and faster transport of electrons.
Therefore, the higher electron concentration in the conduction
band and the reduction of recombination rate resulted in the
improvement of Voc. In addition, for doped ZnO lms higher
values of ll factor are obtained due to the suppressed charge
recombination at the perovskite/ZnO lm or HTM/ZnO lm
interface. Fig. 10b shows the comparison of IPCE spectra for
pure and Al-doped ZnO lms. Jsc for both cells accurately
corresponds to integrating the IPCE spectrum. The cells based
on Al-doped ZnO lms show a slightly enhanced square spectral
response compared to cells with pure ZnO lms having an
eciency of greater than 80% in the entire wavelength ranging
from 370 nm to 750 nm. These results conrm that the Aldoping into the ZnO sites is helpful to enhance the PCE due to
the reduced charge recombination at the ZnO lm interface.

4. Conclusions
The basic process variables in the electrospraying method
which can control the morphology of ZnO thin lms are
substrate temperature, precursor solution ow rate (droplet
size), substrate-to-nozzle distance, applied voltage and deposition time. The parameters such as solution ow rate, substrate
temperature and substrate-to-nozzle distance are dependent on
each other since they all aect the quantity and evaporation of
spraying solution over the surface of the substrate. Both the
substrate-to-nozzle distance and ow rate control the solution
amount approaching the substrate surface. In addition, the
substrate temperature is very helpful to nally control the
morphology of the lm by the adjustment of variation between
these two parameters. The most appropriate conditions for
good quality of ZnO lms are either a long distance or low
solution ow rates. Moreover, the substrate temperature should
be controlled accordingly. For our case, continuous and dense
lms have been obtained at an optimized ow rate of 0.003 mL
min1 and at a distance of 4 cm which can produce a higher
PCE compared with other lms. For these lms the substrate
temperature ranged from 150 to 170  C. Practically, the
temperature window for the given deposition parameters is
approximately 10 to 20  C and the temperature window

This journal is The Royal Society of Chemistry 2014

becomes narrow in the case where a larger distance and/or


larger ow rates are used. The ZnO lms produced under the
optimized process conditions are employed as photoanodes for
ecient perovskite solar cells. An enhanced PCE of 10.8% is
achieved for a 440 nm thick ZnO lm which is the rst study
about using an optimized electrosprayed ZnO lm to the best of
our knowledge. The eciency is mainly dependent on the lm
porosity and smoothness which change by increasing the lm
thickness and ZnO particle size. Furthermore, Al-doped ZnO
lms suppress charge recombination at the ZnO/perovskite
interface which leads to an increase in PCE to 12.0%.
Since the present report emphasizes on the proper utilization of deposition parameters, the same solution was used for
all the cases. Therefore, the discussed lm formation process is
usually applicable; the optimized parameter values are relevant
to this typical precursor solution. The deposition parameters
can be modied when the concentration or the nature of
precursor salts becomes dierent.

Acknowledgements
This work was supported by grants from the National Research
Foundation (NRF), which is funded by the Korean government
(MEST)
(2012M3A7B4049967,
2012M3A6A7054861
and
2014R1A4A1008474).

References
1 A. A. van Zomeren, E. M. Kelder, J. C. M. Marijnissen and
J. Schoonman, J. Aerosol Sci., 1994, 25, 1229.
2 C. H. Chen, M. H. J. Emond, E. M. Kelder, B. Meester and
J. Schoonman, J. Aerosol Sci., 1999, 30, 959.
3 C. H. Chen, E. M. Kelder and J. Schoonman, J. Eur. Ceram.
Soc., 1998, 18, 1439.
4 V. N. Morozov, T. Y. Morozova and N. R. Kallenbach, Int.
J. Mass Spectrom., 1998, 178, 143.
5 R. Festag, S. D. Alexandratos, K. D. Cook, D. C. Joy, B. Annis
and B. Wunderlich, Macromolecules, 1997, 30, 6238.
6 J. Sakata and M. Mochizuki, Thin Solid Films, 1991, 195, 175.
7 N. Fujitsuka, J. Sakata, Y. Miyachi, K. Mizuno, K. Ohtsuka,
Y. Taga and O. Tabata, Sens. Actuators, A, 1998, 66, 237.
8 B. Hoyer, G. Sorensen, N. Jensen, D. B. Nielsen and B. Larsen,
Anal. Chem., 1996, 68, 3840.
9 E. H. Sanders, K. A. McGrady, G. E. Wnek, C. A. Edmondson,
J. M. Mueller, J. J. Fontanella, S. Suarez and S. G. Greenbaum,
J. Power Sources, 2004, 129, 55.
10 N. Dam, M. M. Beerbom, J. C. Braunagel and R. Schlaf,
J. Appl. Phys., 2005, 97, 0249091.
11 H. Fong, I. Chun and D. H. Reneker, Polymer, 1999, 40, 4585.
12 R. Jaeger, H. Schoenherr and G. J. Vancso, Macromolecules,
1996, 29, 7634.
13 C. J. Buchko, L. C. Chen, Y. Shen and D. C. Martin, Polymer,
1999, 40, 7397.
14 V. N. Morozov and T. Ya. Morozova, Anal. Chem., 1999, 71,
3110.
15 J. Li, H. Q. Fan, X. H. Jia, J. Chen, Z. Y. Cao and X. P. Chen,
J. Alloys Compd., 2009, 481, 735739.

Nanoscale, 2014, 6, 91279138 | 9137

View Article Online

Published on 30 June 2014. Downloaded by Sungkyunkwan University on 04/11/2014 09:00:11.

Nanoscale

16 K. Mahmood, H. W. Kang, S. B. Park and H. J. Sung, ACS


Appl. Mater. Interfaces, 2013, 5, 30753084.
17 K. Mahmood and S. B. Park, J. Mater. Chem. A, 2013, 1, 4826
4835.
18 K. Mahmood, H. W. Kang, R. Munir and H. J. Sung, RSC Adv.,
2013, 3, 2513625144.
19 K. C. Park, D. Y. Ma and K. H. Kim, Thin Solid Films, 1997,
305, 201209.
20 J. Ma, J. Feng, D.-H. Zhang, H.-L. Ma and S.-Y. Li, Thin Solid
Films, 1999, 357, 98.
21 S. H. Jeong, J. W. Lee, S. B. Lee and J.-H. Boo, Thin Solid
Films, 2003, 435, 78.
22 S. H. Jeong, S. Kho, D. Jung, S. B. Lee and J.-H. Boo, Surf.
Coat. Technol., 2003, 174, 187.
23 S. Muthukumar, C. R. Gorla, N. W. Emanetoglu, S. Liang and
Y. Lu, J. Cryst. Growth, 2001, 225, 197201.
24 M. de la L. Olvera, A. Maldonado, R. Asomozaa and
M. Melendez-Lira, Sol. Energy Mater. Sol. Cells, 2002, 71,
6171.
25 Y. W. Sun, J. Gospodyn, P. Kursa, J. Sit, R. G. DeCorby and
Y. Y. Tsui, Appl. Surf. Sci., 2005, 248, 392396.
26 A. E. Jimenez-Gonzalez, J. A. Soto Urueta and R. SuarezParra, J. Cryst. Growth, 1998, 192, 430438.
27 K. Mahmood, D.-S. Song and S. B. Park, Surf. Coat. Technol.,
2012, 206, 47304740.
28 J. Burschka, N. Pellet, S.-J. Moon, R. Humphry-Baker, P. Gao,
M. K. Nazeeruddin and M. Gr
atzel, Nature, 2013, 499, 316
319.
29 L. Etgar, P. Gao, Z. Xue, Q. Peng, A. K. Chandiran, B. Liu,
M. K. Nazeeruddin and M. Gr
atzel, J. Am. Chem. Soc., 2012,
134, 1739617399.
30 H. S. Kim, J. W. Lee, N. Yantara, P. P. Boix, S. A. Kulkarni,
S. Mhaisalkar, M. Gr
atzel and N. G. Park, Nano Lett., 2013,
13, 24122417.
31 H.-S. Kim, C.-R. Lee, J.-H. Im, K.-B. Lee, T. Moehl,
A. Marchioro, S.-J. Moon, R. Humphry-Baker, J.-H. Yum
and J. E. Moser, Sci. Rep., 2012, 2, 591.
32 M. M. Lee, J. Teuscher, T. Miyasaka, T. N. Murakami and
H. J. Snaith, Science, 2012, 338, 643647.
33 M. Liu, M. B. Johnston and H. J. Snaith, Nature, 2013, 501,
395398.

9138 | Nanoscale, 2014, 6, 91279138

Paper

34 J. Qiu, Y. Qiu, K. Yan, M. Zhong, C. Mu, H. Yan and S. Yang,


Nanoscale, 2013, 5, 32453248.
35 D. Sabba, H. M. Kumar, N. Yantara, T. T. T. Pham,
N.-G. Park, M. Gratzel, S. G. Mhaisalkar, N. Mathews and
P. P. Boix, Nanoscale, 2014, 6, 16751679.
36 M. H. Kumar, N. Yantara, S. Dharani, M. Graetzel,
S. Mhaisalkar, P. P. Boix and N. Mathews, Chem. Commun.,
2013, 49, 1108911091.
37 D. Bi, G. Boschloo, S. Schwarzmuller, L. Yang,
E. M. J. Johanssona and A. Hagfeldt, Nanoscale, 2013, 5,
1168611691.
38 D.-Y. Son, J.-H. Im, H.-S. Kim and N.-G. Park, J. Phys. Chem.
C, 2014, DOI: 10.1021/jp412407j.
39 F. J. Ramos, M. C. Lopez-Santos, E. Guillen,
M. K. Nazeeruddin, M. Gr
atzel, A. R. Gonzalez-Elipe and
S. Ahmad, ChemPhysChem, 2014, 15, 11481153.
40 K. Mahmood, R. Munir, B. S. Swain, G.-S. Han, B.-J. Kim and
H. S. Jung, RSC Adv., 2014, 4, 90729077.
41 K. Mahmood and S. B. Park, Electron. Mater. Lett., 2013, 9,
161170.
42 D. Liu and T. L. Kelly, Nat. Photonics, 2014, 8, 133138.
43 J. Woosley, R. Turnbull and K. Kim, J. Appl. Phys., 1988, 64,
4278.
44 S. Koombhongse and D. H. Reneker, J. Appl. Phys., 2001, 90,
48364846.
45 V. N. Morozov, T. Y. Morozova and N. R. Kallenback, Int.
J. Mass Spectrom., 1998, 178, 143159.
46 Y. M. Shin, M. M. Hohman, M. P. Brenner and
G. C. Rutledge, Polymer, 2001, 42, 99559967.
47 J. M. Deitzel, J. Kleinmeyer, D. Harris and N. C. Beck Tan,
Polymer, 2001, 42, 261272.
48 C. Chen, Thin-lm components for lithium-ion batteries, PhD
thesis, Del University of Technology, 1998.
49 C. Chen, K. Varhaug and J. Schoonman, J. Mater. Syn. and
Proc., 1996, 3, 189194.
50 N. Stelzer and J. Schoonman, J. Mater. Syn. and Proc., 1996, 4,
429438.
51 J. H. Jeong, Y. S. Jeon, K. K. Jeon, K. S. Hwang and B. H. Kim,
J. Ceram. Process. Res., 2006, 7, 7074.

This journal is The Royal Society of Chemistry 2014

You might also like