33rd European Photovoltaic Solar Energy Conference and Exhibition
STRUCTURAL, OPTICAL AND ELECTRICAL PROPERTIES OF ZNO/PEROVSKITE/CUO/ AL SOLAR
CELLS
H.Ait Dads12*, L. Nkhaili1, A. Kissani1, H. El AAkib12, S. Laalioui1, M. Ait Ali2, A. Outzourhit1
1Nanomaterials Laboratory for Energy and Environmental, Faculty of Sciences Semlalia, Cadi Ayyad
University, Marrakech, Morocco.
2Laboratory of Coordination Chemistry and Catalysis, Faculty of Sciences Semlalia, Cadi Ayyad
University, Marrakech, Morroco
ABSTRACT: Organolead-halide-perovskite-based solar cells have recently received significant attention due to their
excellent photovoltaic performances and low cost. The general formula of the perovskite absorber is ABX3, where A
stands for (R-NH3) and B is a metal (Pb or Sn) and X is a halide (Cl, I, or Br).
In this work we report on the fabrication of FTO/ ZnO/ CH3NH3Pb(I1-xBrx)3 /CuO/Al planar heterojunction solar
cells. The perovskite acts as an absorber, CuO and ZnO act as a hole conductor and electron transport layers
respectively. The perovskite was produced by a two step process in ambient atmosphere. Zinc oxide thin films and
copper oxide were fabricated by RF sputtering on indium- tin- oxide covered glass substrates. The structural and
optical properties of the films were analyzed by X-ray diffraction, and ultraviolet-visible spectroscopy. The electrical
junction properties were investigated by current–voltage (I–V) characteristics. The junction showed a photovoltaic
behavior,
Keywords: metal oxide, heterojunction, RF sputtering, current-voltage (I-V), capacitance-conductance measurements.
1 INTRODUCTION an Ar=O2 gas mixture with 30% of O2. The films were
deposited using an RF power of 200W for 30min. These
Over the past few years, thin film solar cells based on parameters were obtained from a previous optimization
organic-inorganic lead trihalide perovskite absorbers of the deposition conditions [4][5][6][7].
have experienced an unexpected breakthrough and rapid 2.3. Preparation of CuO Films
progress in cell performance. To date, these perovskite Copper oxide thin films were prepared by reactive RF
thin film solar cells have exclusively employed organic sputtering substrates at room temperature from a Cu
hole conducting polymers which are are normally quite target (5N purity, 10cm diameter). There active
expensive due to complicated synthetic procedure or sputtering was carried out in Ar =O2 gas mixture with
high- purity requirement[1] [2]. In a quest to explore new 30% of O2. The films were deposited at an RF power of
inorganic hole conducting materials . 150W for 90min [8] [9][10][11].
For these perovskite based thin film photovoltaics, The top Al circular electrode was fabricated by
we have identified copper oxide as a possible alternative. thermal evaporation at 2.10-5 mbar base pressure. The
Here in we demonstrate a device structure consicting of thickness of this Al layer is about 100 nm.
Zno as electron collector, lead halide perovskite as the 2.4. Characterization techniques
light harvester and CuO as the Htm. The combination of The structural properties were investigated by X-ray
CH3NH3PB(I1-xBrx)3 with CuO show high PCE of diffraction with an X-pert MPD diffractometer ( using the
3,32%.. CuKα radiation. The surface morphology of the as-
prepared samples was studied by atomic force
microscopy. Optical transmittance measurements were
2 EXPERIMENTAL STUDY performed using a Shimadzu UV-PC spectrophotometer
in the 200 - 3200 nm range.
2.1 Synthesis of perovskite CH3NH3PB(I1-xBrx)3 The current-voltage (I-V) characteristics of FTO/
For the perovskite layer, PbI2 and PbBr2 were ZnO/ CH3NH3Pb(I1-xBrx)3 /CuO/Al were measured at
dissolved in DMF, dropped onto the ZnO film and spin room temperature using a Keithley LCZ3000 meter and
coated followed by annealing at 90 C for 30 min. In the Keithley 410 programmable ammeter and voltmeter
second step, the cell was dipped into the dipping solution
of MAI in isopropanol. Following the dipping step, the 3 RESULTS And DISCUSSION
samples were annealed at 100°C for 30 min, [3]
The XRD patterns of the Zno thin films present only
2.2 Deposition of ZnO Layer one peak at 2O=34.1° (figure 1), corresponding to the
The ZnO thin films were prepared by reactive RF- (002) diffraction peak of the hexagonal wurtzite phase of
sputtering. These films were deposited using a high purity ZnO. This suggests that the films have a preferred growth
Zn metal target with a diameter of 10cm in an argon orientation in the (002) direction.
oxygen gas mixture. Prior to the deposition, ITO
substrates were ultrasonically cleaned in acetone and
isopropyl alcohol followed by deionized water to remove
any impurities and then rinsed with deionized water. The
substrates were then mounted at a distance of 10cm
above the Zn target (5N: purity, diameter: 10cm). The
vacuum chamber was evacuated to a final pressure of
1.5 10-6 mbar. The target was presputtered for 10min,
and the substrates were not intentionally heated during `
the deposition. The reactive sputtering was carried out in
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33rd European Photovoltaic Solar Energy Conference and Exhibition
600nm. The absorption α coefficient was evaluated from
these data. The inset of figure 4 shows the plot of the
conventional Tauc equation (α hv)n = A(hv-Eg) where A
is an empirical constant, h α is the photon energy and n=2
for the direct band gap semiconductor. By extrapolation
of the part of the (α hv)n vs.hv plots. We found that the
Eg value for this compound is 1.76 eV. [12][13]
Figure 1: XRD- pattern of zinc oxide thin film
deposited on indium tin oxide
Figure 2 shows the optical transmittance spectra of
ZnO thin films in the wavelength range from 300 to 2000
nm. The films are highly transparent in the visible range of
the electromagnetic spectrum with an average
transmittance values up to 84 %.
The optical band gap of the films was determined from
the variations of the absorption coefficient with photon
energy and by assuming direct transitions. Details Figure 4: Optical transmission of perovskite
concerning the determination of thèse parameters from the deposited on glass substrate
optical transmission Spectrum were reported by [8]. The
optical band gap Eg were found to be 3.28 eVThe value of The XRD pattern of CuO thin film was shown in
the optical gap of our films is in agreement with reported figure 5 and it revealed that the as-deposited film present
values. [8]. the (111), (111), (220) and (113) diffraction peaks that
are characteristic of the monoclinic phase CuO
[24][25][26] .
Figure 2: Optical transmission of zinc oxide deposited
on indium tin oxide
GIXRD measurement was firstly conducted to Figure 5: XRD- pattern of CuO thin film deposited
confirm the film crystal structure and the diffraction on glass substrate
pattern is shown in Figure 3. Besides a tiny signature
peak at 12.60º corresponds to a low-level impurity of The optical transmission of a typical as-deposited
PbI2, [4] the intense peaks can be respectively assigned CuO film is shown in Figure 6. In this case, the average
to 110, 112, 202, 220, 312, 240, 224 and 314 planes of a transmission in the visible range is around 60%. The
perovskite structure. Compared to CH3NH3PbI3, the presence of interference fringes is an indication of the
diffraction peaks of CH3NH3PB(I1-xBrx)3 are shifted good quality and the smoothness of the surface of the
uniformly to high angles, which can be caused by the films. The transmission was used to evaluate the
replacement of I by Br. [4][12][13] absorption coefficient in the spectral range below the
absorption edge. The latter was used to determine the
optical gap Eg,by assuming a direct band gap
semiconductor. The optical band gap of the films was
found to be 1.8eV.[9][10][11]
Figure 3: XRD- pattern of perovskite thin film
deposited on glass substrate
Figure 4 shows the optical transmittance of
perovskite film spin coated on glass substrate. The optical
transmission of the as-prepared CH3NH3Pb(I1-xBrx)3 thin Figure 6: Optical transmission of CuO deposited on
films show a sharp drop in the transmission below glass substrate
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33rd European Photovoltaic Solar Energy Conference and Exhibition
Figure 7 presents the J–V curve of the hybrid solar Outzourhit Structural, optical and electrical properties of
cell with an FTO/Zno/ CH3NH3PB(I1-xBrx)3 / CuO/Al planar mixed Perovskite halides/ Al-doped Zinc oxide
structure. IUnder illumination the solar cell show a solar cells. Sol Ener Mater Sol Cells (2015)
photovoltaic behavior and has provided the highest power [5] Yinzken, W.; Benli, C. Effects of sapphire substrates
conversion efficiency (η) of 3.22%, a fill factor (FF) of surface treatment on the ZnO thin films grown by
0.5, an open-circuit voltage (VOC) of 0.5 V and a lower magnetron sputtering. Phys B2008, 403, 1979.
Is= 3.31 nA. The low ISC suggest that the high resistivity [6] Kuroyanagi, A. Properties of aluminum-doped ZnO
of ZnO and CuO layers is the main factor that limits the thin films grown by electron beam evaporation. App
cell performance. Phys, 28, 219. (1989)
[7] L.Nkhaili, A. El kissani, M. Ait Ali, Y.
Ijdiyaou, A.Elmansouri, A. Elkhalfi, A. Outzourhit Effect
of RF power on the structural and optical properties of
RF-sputtered ZnO thin films
Eur. Phys. J. Appl. Phys. (2014) 66: 30302
[8] Izhizuka, S.; Kato, S.; Maruyama, T.; Akimoto, K.
Nitrogen doping into Cu2O thin films deposited by
reactive radiofrequency magnetron sputtering. Appl Phys,
40, 2765–2768, (2001)
[9] .B. Balamurugan and B. R. Mehta, “Nanocrystalline
Thin Films, Optical Properties. Structural Properties. X-
Ray Diffraction,” Thin Sol Fil, Vol. 396, No. 1-2,
Figure 7: Current -Voltage characteristics of ZnO/ (2001), pp. 90-96.
CH3NH3PbI( (1- x)Brx)3 / CuO/Al cells
[10] F. Marabelli, G. B. Parraviciny and F. S. Orioli,
4 CONCLUSION “Optical Gap of CuO,” Phys Revi B, Vol. 52, No. 3,
(1995), pp. 1433-1436.
CH3NH3PB(I1-xBrx)3 thin films were successfully
fabricated by sequential deposition which consist on spin [11] J. Ghijsen, L. H. Tjeng, J. V. Elp, H. Eskes, J.
coating a solution obtained by mixing lead iodide and Westerink, G. A. Sawatzky and M. T. Czyzyk,
lead bromide PbBr2 on ZnO film, the cell was then “Electronic Structure of Cu2O and CuO,” Phys Rev B,
dipped into the dipping solution of MAI in isopropanol . Vol. 38, No. 16, (1988), pp. 11322-11330.
X-ray diffraction and optical transmission measurements [12] W. A. Laban and L. Etgar, Retarding the
confirmed the formation of a single-phase mixed crystallization of PbI2 for highly reproducible
perovskite that is suitable for an absorber layer in planarstructured perovskite solar cells via sequential
Tandem cells. The optical band gap of perovskite thin deposition. Ener. Environ. Sci., ( 2013), 6, 3249.
films is 1.76 eV. The as-deposited films of ZnO and CuO
were polycrystalline with quasi-uniform grain size. The
ZnO films exhibited a (002) preferred growth orientation
on glass substrates while CuO films did not exhibit this
feature. The average optical transmission of the ZnO
films is on the order 80% while its only 60% for
CuO.The optical bandgaps of the obtained CuO and ZnO
films are found to be 1.8 and 3.28 eV respectively. The
high transmittance of the as-prepared ZnO films in the
visible range makes them very suitable as window layer
in solar cells. The optical bandgap of the as-prepared
CuO films, on the other hand, is more suitable for solar
cells than that of CuO2.
The ZnO/ CH3NH3PB(I1-xBrx)3 / CuO/Al
heterojunction showed a solar cell behavior, The
photocurrent was observed under illumination at 480
mW•cm−2 and the solar cell showed a conversion
efficiency of 3,22%.The obtained cell parameters low
Icc indicating the need of limiting the resistivity of ZnO
and CuO films.
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[2] Liu, M., Johnston, M. B. & Snaith, H. J. Efficient
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deposition. Nat 501, 395–398 (2013)
[3] Burschka, J. et al. Sequential deposition as a route to
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[4] H.Ait DADS, S.Bouzit, L. Nkhaili, A. Kissani, A.
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