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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
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
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(ESI)
available.
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DOI:
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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
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2.
Experimental
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Fig. 1
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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
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3.
Paper
Paper
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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
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
Nanoscale
Paper
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.
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.
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.
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
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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.
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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
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Film type
PCE*a (%)
Voc (%)
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.
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
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.
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