Cite this article Research Article Keywords: characterisation/fabrication/

Verma AK, Shukla N and Tiwari S Paper 1800021 solar cells

Effect of ZnO ETL and MoO3 HTL with PCDTBT:PC70BM-based BHJ organic solar cells. Received 11/12/2018; Accepted 01/09/2020
Nanomaterials and Energy,
https://doi.org/10.1680/jnaen.18.00021 ICE Publishing: All rights reserved

Nanomaterials and Energy

Effect of ZnO ETL and MoO3 HTL with

PCDTBT:PC70BM-based BHJ organic solar cells
Anil Kumar Verma MSc, NET Naman Shukla MTech, NET
PhD scholar, School of Studies in Electronics and Photonics, Pt. Ravishankar PhD scholar, School of Studies in Electronics and Photonics, Pt. Ravishankar
Shukla University, Raipur, India (Orcid:0000-0003-2955-8967) Shukla University, Raipur, India (Orcid:0000-0002-7133-9912)
(corresponding author: [email protected]) Sanjay Tiwari PhD
Professor and Head, School of Studies in Electronics and Photonics, Pt.
Ravishankar Shukla University, Raipur, India (Orcid:0000-0003-0794-9457)

In this work, the authors fabricated and characterized efficient inverted organic solar cells by modifying them with a
highly transparent sol–gel-derived zinc oxide (ZnO) film as an electron transport layer and optimized molybdenum
trioxide (MoO3) as a hole transport layer with a very low-bandgap polymer, poly[N-900-hepta-decanyl-2,7-carbazole-alt-
5,5-(40,70-di-2-thienyl-20,10,30-benzothiadiazole)] (PCDTBT), in bulk heterojunction (BHJ) composites with the fullerene
derivative [6,6]-phenyl-C70-butyric acid methyl ester (PC70BM) BHJ in various solvents. Variations in the sol concentration,
thickness, surface and optical characteristics of inverted organic solar cell glass/indium tin oxide/zinc oxide/PCDTBT:
PC70BM/molybdenum trioxide/silver (Ag) structures were investigated and analyzed. The thickness of zinc oxide increased
as the sol concentration increased from 10 to 100 nm. With the modification of the PCDTBT:PC70BM solvent, the device
efficiency improved from 4.22 to 7.43%, which was accompanied by an improvement in the open-circuit voltage (Voc)
from 0.87 to 1.03 V and enhancement of the short-circuit current density (Jsc) from 9.1 to 13.5 mA/cm2.

Notation configuration includes an electron transport layer (ETL) inducing

Jsc short-circuit current density effective electron collection at the ITO anode and a hole transport
Rs series resistance layer (HTL) leading to efficient hole collection at the top cathode.
Rsh shunt resistance
Voc open-circuit voltage The advance of bulk heterojunction (BHJ) OSCs promises to
h efficiency show better improvement.14–20 Power conversion efficiencies
(PCEs) of up to 8% have been already reported.21–26 However,
1. Introduction for global commercialization, further improvements in PCE and
Organic solar cells (OSCs) or polymer solar cells have potential stability are needed. A BHJ OSC generally consists of a
as a competitive photovoltaic (PV) technology for large-area, transparent anode contact (typically ITO), a BHJ active layer (a
flexible, durable and very low-cost power generation blended mixture of donor polymer and fullerene molecule
applications.1,2 A very attractive feature of organic PVs is the acceptor) and a cathode (e.g. aluminum (Al) or silver (Ag)).
possibility of realizing semitransparent cells. Owing to the ETLs/HTLs are used as charge-selective contacts between the
pronounced absorption features of various absorber molecules BHJ active layer and the electrodes.27,28 Many experiments have
used in OSCs, devices can be designed to transmit light within a shown that the lifetime of BHJ solar cells can be increased by
specific spectral range. Meanwhile, colored see-through PV introducing an HTL such as titanium dioxide (TiO2) or lithium
elements (e.g. windows) can be made possible. In combination fluoride (LiF) between the BHJ layer and the cathode.29–31
with semitransparent organic light-emitting diodes (LEDs),3 the
emerging applications come within reach of industry and the In the past decades, various methods, device materials and
market. As opposed to standard OSCs used for the preparation of structures have been reported for improvements of inverted BHJ
semitransparent organic devices, one of the key issues is related to OSCs. Cheng et al.32 used efficient BHJ poly(3-hexylthiophene):
the transparent top electrode. There are various methods to (6,6)-phenyl-C61-butyric acid methyl ester (PCBM) solar cells
deposit thin films for transparent electrodes on thermally with molybdenum trioxide (MoO3) and copper phthalocyanine
evaporated thin metal films or a multilayer of thin metal films and (CuPc) as buffer layers. The use of a molybdenum trioxide layer
sputtered indium tin oxide (ITO) layers.4–6 was found to be critical in device performance, as the layer
effectively pulls holes to prevent exciton quenching and reduction
Research studies on inverted device structures with a reversed of the interfacial resistance due to the alignment of energy levels.
charge-collecting nature at the electrodes have also been a new Cheng et al.32 studied the effect of the molybdenum trioxide and
engineering idea for the development of highly efficient and CuPc layer thickness on device performance. When the thickness
stable OSCs resulting from the placement of poly(3,4- of the molybdenum trioxide layer was 12 nm and that of the CuPc
ethylenedioxythiophene) (Pedot):polystyrene sulfonate (PSS) and layer was 6 nm, the resulting optimized PCE was 3.76%.32 There
low-work-function metal electrodes.7–13 The general inverted have been significant efforts and enormous progress in the field of

1
Downloaded by [ University of Melbourne] on [31/10/20]. Copyright © ICE Publishing, all rights reserved.
 Nanomaterials and Energy Effect of ZnO ETL and MoO3 HTL with
PCDTBT:PC70BM-based BHJ organic
solar cells
Verma, Shukla and Tiwari

nanoparticle (NP) research regarding the synthesis of metal oxide studies showing that a higher efficiency is achieved with an active
particles, allowing one to predict precisely the composition, layer thickness of up to 200 nm. Thus, the authors optimized the
structure, size, form and optoelectronic properties. Metal-oxide optimum 80 nm thickness of PCDTBT:PC70BM photoactive
semiconductor nanocrystals based on sol–gel synthesis routes, layers.39 First, the authors observed that the efficiency of inverted-
such as zinc oxide (ZnO), titanium dioxide and s-molybdenum structure OSCs was enhanced with a highly transparent sol–gel-
trioxide, have attracted intensive interest during the last few years, derived zinc oxide ETL by varying and controlling the
because their outstanding optical and electrical properties qualify concentration of the sol. In addition, replacing the commonly
them for multiple optoelectronic applications, particularly for thin- used Pedot:PSS with zinc oxide helps increase the fill factor
film solar cells. Efficient solar cells with MoO3 interface layers (FF). Second, molybdenum trioxide improved device stability
were reported to have superior environmental stability, paving the without encapsulated PCDTBT:PC70BM such that solar cells
way for the fabrication of more efficient and stable organic BHJ remain intact, even after being kept in the air for several days,
solar cells.33 In another work,34 structures with mainly ITO/ while cells fabricated with other materials such as Pedot:PSS
indium (In)-doped zinc oxide/poly[N-900-hepta-decanyl-2,7- showed rapid degradation. In this work, the authors fabricated
carbazole-alt-5,5-(40,70-di-2-thienyl-20,10,30-benzothiadiazole)] efficient inverted BHJ OSCs using a sol–gel-derived zinc oxide
(PCDTBT):[6,6]-phenyl-C71-butyric acid methyl ester (PC71BM)/ electron-selective layer and a molybdenum trioxide-selective
molybdenum trioxide/aluminum were successfully fabricated. The layer. Thermally evaporated molybdenum trioxide thin films with
inverted OSCs with 6.74% In-doped ZnO exhibited a maximum a thickness of 10 nm were deposited as cathode interfacial layers.
PCE of 5.58%, which is the best efficiency reported so far for
these types of solar cells. The device performance was optimized 2. Device structures
by varying the indium doping concentration. Thus, the authors In this work, inverted device structures, glass/ITO/zinc oxide/
achieved the PCE by incorporating indium into the zinc oxide PCDTBT:PCBM/silver, were stacked from bottom to top, as
films.34 Two years later, the stability of PCDTBT:PC71BM-based shown in Figure 1(a). The energy level diagram of the inverted
BHJ OSCs for over the course of a year was investigated, and it device structure is presented in Figure 1(b).
was concluded that in the most stable devices, the observed
lifetime is limited by the thermally induced stress between the 3. Experimental methods and device
device layers, as well as material degradation as a result of edge fabrication
ingress of water or moisture through the encapsulation.35 The The ITO substrate was prepared through the following procedure:
purpose of the present work is to enhance the efficiency and ITO-coated glass substrates were prepared in 12.5 mm2 sizes by
stability of BHJ inverted OSC devices with PCDTBT:[6,6]- removing a 2 mm ITO glass (purchased from Techinstro) pattern
phenyl-C70-butyric acid methyl ester (PC70BM) active material for the contact using ultraviolet (UV) treatment for 10 min. The
employing zinc oxide as the ETL and molybdenum trioxide as the patterned ITO was cleaned by ultrasonication with soap water,
HTL by optimization and modification. The use of zinc oxide and deionized water, acetone and isopropyl alcohol for 10 min each.
molybdenum trioxide provides both stability and transparent The completely cleaned ITO substrates were dried on a hot plate
layers for the devices. More specifically, the primary aim of the and subsequently treated by using a plasma asher for 10 min to
fabrication efforts of interest in this work is to fabricate accurately remove oxide contamination. The plasma-treated ITO substrates
the device properties of BHJ solar cells and hence optimize the were directly transferred into a spin coater for pre-prepared
efficiency of BHJ OSC devices. First, the physics involved in the sol–gel zinc oxide solution deposition. Sol–gel zinc oxide
functioning of BHJ PVs was investigated. Then, fabrication and solutions were synthesized and prepared as discussed in the
characterization of devices of inverted BHJ OSCs were carried literature.40–42 For preparing zinc oxide thin films, the authors
out. Afterward, results of measurements of the thickness, surface used zinc acetate dihydrate (Zn(CH3COO)2·2H2O; 99.9%,
topography and optical and electrical characteristics of PCDTBT: Sigma-Aldrich). Zinc acetate dihydrate was dissolved in
PC70BM BHJ inverted OSCs are presented. Finally, the work 2-methoxyethanol anhydrous (C3H8O2; 99.8%, Merck) to prepare
ends with conclusions. zinc oxide sol, and ethanolamine (MEA) (NH2CH2CH2OH;
99.9%, Sigma-Aldrich) was added dropwise to obtain
Furthermore, ETLs (e.g. titanium dioxide or zinc oxide) also homogeneous and transparent sols. Consequently, the prepared
function to reorganize the light intensity inside the BHJ active sols with varying concentrations of precursors were spin-coated
layer, thus enhancing the harvesting of light energy.36–38 The on pre-patterned ITO glass substrates.
authors observed that the use of zinc oxide as the ETL improved
the PCE and significantly increased both the device lifetime and BHJ OSCs with inverted structures were fabricated on the ITO
stability. The authors carefully chose molybdenum trioxide for in- substrates as discussed earlier. An active layer with a thickness of
depth studies because of its good transmittance as well as wide around 80–90 nm was deposited by spin-coating a solution of
bandgap and easy fabrication using thermal evaporation PCDTBT:PC70BM (1:4) dissolved in chlorobenzene (CB) and
techniques. BHJ solar cells fabricated with PCDTBT:PC70BM as dichlorobenzene (DCB) on top of the pre-spin-coated ITO/zinc
the photoactive layer, zinc oxide as the ETL and molybdenum oxide samples. Just after the spin-coating of the active layer
trioxide as the HTL show better performance. There are various solution, the samples were transferred to hot plates for annealing

2
Downloaded by [ University of Melbourne] on [31/10/20]. Copyright © ICE Publishing, all rights reserved.
 Nanomaterials and Energy Effect of ZnO ETL and MoO3 HTL with
PCDTBT:PC70BM-based BHJ organic
solar cells
Verma, Shukla and Tiwari

–2.6 eV
+
–3.4 eV
– V
Ag –3.8 eV

–4.3 eV
PCDTBT MoO3
MoO3 HTL
PCDTBT:PC70BM –4.2 eV
–4.8 eV
ZnO ZnO PCBM Ag
ITO ITO
Glass substrate –5.3 eV
–5.6 eV

–6.2 eV

–7.7 eV

(a) (b)

Figure 1. (a) Device structure of PCDTBT:PCBM inverted BHJ OSCs; (b) energy level diagram of the proposed inverted device structure

at 70°C for 10 min and by covering the sample using a petri dish, 4. Results and discussion
so that the solvent was slowly evaporated. After the sample had It is possible that the improvement in the device performance is due
been completely dried, it was ready for deposition of a to the proper thickness and better surface quality of the film, which
molybdenum trioxide HTL with an optimal thickness of 10 nm. provides better wettability and adhesion with the photoactive layer.
Subsequently, a silver cathode layer with a thickness of 100 nm Therefore, thickness optimization, surface roughness, structural
was deposited on top of molybdenum trioxide by thermal morphology, absorbance and semicrystallinity analysis were carried
evaporation in a vacuum system with a pressure of 10−6 mbar. All out to investigate the surface quality of each film mainly composed
these fabrication processes were carried in a glove box at Organic of zinc oxide and PCDTBT:PC70BM layers.
Electronics Laboratory, Indian Institute of Technology, Bombay,
under an Indian Nanoelectronics User Program-funded program. The thickness was optimized and confirmed by using a Dektak
The typical active cell area of the devices fabricated in this work profilometer. Atomic force microscopy (AFM) measurements of the
was taken to be around 0.045 cm2 by using a metal shadow mask zinc oxide and PCDTBT:PC70BM thin films were carried out, and
during the evaporation of the cathode (silver). The authors used the results are shown in Figures 2(a)–2(c) and 3(a)–3(c), respectively.
epoxy to stick and UV treatment for curing for 10 min. The The zinc oxide thin films were made up of a large number of peaks
voltage–current (V–I) characteristics were taken using a Keithley that grew in size as the film thickness was increased. In XRD peaks
2400 source meter under an illumination of simulated AM1.5 the contact area between PCDTBT:PC70BM and molybdenum
sunlight with an intensity of 100 mW/cm2 provided by an LED trioxide may generate and allow for efficient hole collection. AFM
solar simulator (LSH-7320, class ABA type), whose intensity was images of the surface of the studied films confirm a remarkable
calibrated by using a standard single-crystal silicon (Si) solar cell. change in the morphology of the film. Figure 2 shows the AFM

385.42 nm 331.46 nm 265.67 nm

2.0 µm 2.0 µm 2.0 µm

0 nm 0 nm 0 nm
(a) (b) (c)

Figure 2. AFM images of zinc oxide films with (a) 0.1, (b) 0.2 and (c) 0.5 M concentrations on glass/ITO samples

3
Downloaded by [ University of Melbourne] on [31/10/20]. Copyright © ICE Publishing, all rights reserved.
 Nanomaterials and Energy Effect of ZnO ETL and MoO3 HTL with
PCDTBT:PC70BM-based BHJ organic
solar cells
Verma, Shukla and Tiwari

33.92 nm 34.46 nm 38.24 nm

400 nm 400 nm 400 nm

0 nm 0 nm 0 nm
(a) (b) (c)

Figure 3. AFM images of PCDTBT:PC70BM films with (a) 0.1, (b) 0.2 and (c) 0.5 M concentrations on glass/ITO samples

images of zinc oxide thin film on ITO glass samples at different 10 min was studied with SEM, and the SEM image is shown in
concentrations of 0.1, 0.2 and 0.5 M with a scanning area of 1 mm2. Figure 4. In Figure 4, it can be seen that the prepared particles
The roughness of the film increased with increasing concentration. formed clusters. The underlying mechanism of this behavior is that
Figure 3 shows the AFM images of PCDTBT:PCBM samples on as the sol–gel concentration increases, the amount of solutes in the
zinc oxide/ITO glass substrates. The roughness of the film decreased sol increases, thereby increasing the probability of solutes clustering
on thermal annealing, showing more pronounced peaks, which can together, forming larger grains.44 The grain size revealed from the
be possible evidence of growing units of donor and acceptor SEM image is consistent with surface roughness measurement and
materials. However, it is not so easy to conclude anything precisely larger grain size results for rougher film, and the crystallite size of
from the AFM images, since these show only the topography of the the annealed thin films is in the range 20–80 nm diameter.
top film surface. These results confirmed that slow growth of the
films can modify the crystalline structure of sol–gel zinc oxide and High-resolution X-ray diffraction patterns were recorded in this
PCDTBT:PCBM polymer and the ordering of the interface work to identify crystalline phases and to estimate the crystalline
arrangement of the bulk. Moreover, it was also observable that just sizes; the patterns are shown in Figures 5(a) and 5(b). These
thermal annealing was required for complete improvement of the results show the XRD peaks for different thicknesses and
device performance. concentrations of zinc oxide thin films on ITO glass annealed at
200°C for 10 min each. These show the semicrystalline structure
The root-mean-square (RMS) and average roughness were analyzed of zinc oxide. When sunlight falls on the glass/ITO side, the
by using the WSxM 5.0 Pro Software.43 The RMS and average absorbance of the photoactive layer is essential in understanding
roughness of zinc oxide and PCDTBT:PC70BM films are high-performance OSC devices. Basically, the absorbance
summarized in Table 1. Further, for surface and roughness
characterization, scanning electron microscopy (SEM) of zinc oxide
films deposited from different concentrations of sols was carried
out. The films were composed of nano-sized zinc oxide colloids,
and the grain size increased with the increase in sol concentration.
The surface RMS roughness of the films obtained from
concentration of the zinc oxide thin films annealed at 200°C for

Table 1. AFM roughness analysis of zinc oxide and PCDTBT:

PC70BM films
RMS Average
Sample name
roughness: nm roughness: nm
Glass/ITO/ZnO_1 0.9191 0.5063
Glass/ITO/Zn0_2 0.8976 0.3953
Glass/ITO/ZnO_3 0.7628 0.5630
Glass/ITO/ZnO/PCDTBT: 0.1580 0.1084 2 µm
PCBM_1
Glass/ITO/ZnO/PCDTBT: 0.1380 0.0966
PCBM_2
Figure 4. SEM image of zinc oxide film deposited on the ITO glass
Glass/ITO/ZnO/PCDTBT: 0.1333 0.0987
substrate
PCBM_3

4
Downloaded by [ University of Melbourne] on [31/10/20]. Copyright © ICE Publishing, all rights reserved.
 Nanomaterials and Energy Effect of ZnO ETL and MoO3 HTL with
PCDTBT:PC70BM-based BHJ organic
solar cells
Verma, Shukla and Tiwari

(100)

(002)

(101)
(103)
*

(200)
(002)
* ZnO 4 * ZnO 4

(103)
*
Intensity: arbitrary units

Intensity: arbitrary units

* *

ZnO 3 ZnO 3

ZnO 2 ZnO 2

ZnO 1 ZnO 1

10 20 30 40 50 60 70 80 10 20 30 40 50 60 70 80
2θ: ° 2θ: °
(a) (b)

Figure 5. XRD patterns for zinc oxide thicknesses of 10, 20, 40 and 60 nm with (a) 0.2 and (b) 0.5 M concentrations. *, unknown value;
ZnO 1, zinc oxide 10 nm thick; ZnO 2, zinc oxide 20 nm thick; ZnO 3, zinc oxide 40 nm thick; ZnO 4, zinc oxide 60 nm thick

depends on the material properties and the donor:acceptor The device performance data obtained with a BHJ layer thickness of
concentration. The absorbance spectra of PCDTBT:PC70BM with 80 nm are summarized in Table 2. The optimal thicknesses of zinc
1:4 concentration are shown in Figure 6. From the absorption oxide and molybdenum trioxide were confirmed to be 40 and 10 nm,
measurements, one can easily estimate the absorption and optical respectively. This device shows a maximum PCE = 4.22%, a short-
bandgap of the absorbing materials. The absorption spectrum circuit current Jsc = 9.1 mA/cm2, an open-circuit voltage Voc = 0.86 V
measurements can also help in recording morphological changes and an FF = 0.53. In contrast, the control device (fabricated with the
(e.g. crystallinity of the polymer) in the materials or blends during optimized and modified solvent), as shown in Table 3, has enhanced
device processing (e.g. with different thickness and thermal parameters of PCE = 7.43%, a short-circuit current Jsc = 13.51 mA/
annealing). A UV–visible–near-infrared instrument (Lambda 950) cm2, an open-circuit voltage Voc = 0.98 V and an FF = 0.56. A
was used for analysis of the coatings of thin films. It showed that maximum incident photon conversion efficiency of around 56% for
the PCDTBT:PC70BM polymer material has wide absorbance of the device was achieved. In the literature, various research groups
light around 450–680 nm wavelength. have also achieved significant results in this field for the HTL,
photoactive layer and ETL for efficient device performance of BHJ
The current density–voltage (J–V) characteristics and external OSCs. A comparison of some of the novel works reported in the
quantum efficiency (EQE) spectra of the PCDTBT:PC70BM blend in literature is summarized in Table 4.21,39,45 The maximum PCE
CB and DCB solvents in inverted OSCs fabricated with zinc oxide reported in the literature has been found to be approximately 5.96%.21
ETL and molybdenum trioxide HTL are shown in Figures 7(a)–7(d). Thus, the authors have successfully achieved a promising result,
which is a higher PCE value than that in the literature using the
PCDTBT:PC70BM absorber photoactive layer based on BHJ OSCs.
1.4 × 104

1.2 × 104 5. Conclusions

Absorption coefficient: cm–1

The authors have successfully fabricated and characterized

1.0 × 104 inverted BHJ OSCs with PCDTBT:PC70BM as the active layer
8.0 × 103 showing maximum efficiency approaching 8%. In summary, this
paper presents a simple approach to stabilizing the zinc oxide NP
6.0 × 103 dispersion in the air for the fabrication of stable inverted solar
4.0 × 103 cells with molybdenum trioxide layers. The active layer consisting
of PCDTBT:PC70BM was blade-coated in a glove box
2.0 × 103 environment. The zinc oxide dispersion has a lifetime of more
0 than a month. Within the time window, devices fabricated using
350 400 450 500 550 600 650 700 750 this dispersion have very similar performance. This is a big step
Wavelength: nm
toward the fabrication of large-area and low-cost OSCs in an
industrial setting. A PCE of around 7.43% has been obtained for
Figure 6. UV–visible absorbance spectra of PCDTBT:PC70BM with
1:4 concentration the inverted solar cells with an active area of 0.045 cm2. More
importantly, the non-encapsulated inverted solar cells are quite

5
Downloaded by [ University of Melbourne] on [31/10/20]. Copyright © ICE Publishing, all rights reserved.
 Nanomaterials and Energy Effect of ZnO ETL and MoO3 HTL with
PCDTBT:PC70BM-based BHJ organic
solar cells
Verma, Shukla and Tiwari

40
1
35 ZnO 40 nm
0 ZnO 20 nm
ZnO 40 nm ZnO 60 nm
−1 ZnO 60 nm 30
−2 ZnO 20 nm Chlorobenzene
25
−3

EQE: %
Chlorobenzene
J: mA/cm2

−4 20
−5
15
−6
−7 10
−8
5
−9
−10 0
−0.1 0 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9 300 350 400 450 500 550 600 650 700 750 800
Voltage: V Wavelength: nm
(a) (b)
2 70
0 ZnO 60 nm
ZnO 60 nm 60 ZnO 40 nm
−2 ZnO 40 nm ZnO 20 nm
ZnO 20 nm 50
−4 Dichlorobenzene
Dichlorobenzene
J: mA/cm2

−6
EQE: %

40
−8
30
−10
20
−12

−14 10
−16
0
−0.1 0 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9 1.0 1.1 300 350 400 450 500 550 600 650 700 750 800
Voltage: V Wavelength: nm
(c) (d)

Figure 7. (a) Light J–V characteristics and (b) EQE spectra of devices made from PCDTBT:PC70BM blend with optimized thickness in CB
and different zinc oxide ETL thicknesses; (c) light J–V characteristics and (d) EQE spectra of devices made from PCDTBT:PC70BM blend with
optimized thickness in DCB solvent and different zinc oxide ETL thicknesses

Table 2. Summary of inverted OSC parameters

Device name Voc: V Jsc: mA/cm2 FF: % Rs: W cm2 Rsh: W cm2 PCE: %
Glass/ITO/ZnO/PCDTBT:PC70BM/MoO3/Ag_Device_1 0.86 9.1 53 591 943 4.22
Glass/ITO/ZnO/PCDTBT:PC70BM/MoO3/Ag_Device_2 0.86 8.9 52 517 526 4.10
Glass/ITO/ZnO/PCDTBT:PC70BM/MoO3/Ag_Device_3 0.87 8.4 52 598 1111 3.92

Table 3. Summary of inverted OSC parameters with optimized thickness and solvents
Device name Voc: V Jsc: mA/cm2 FF: % Rs: W cm2 Rsh: W cm2 PCE: %
Glass/ITO/ZnO/PCDTBT:PC70BM/MoO3/Ag_Device_1 1.03 10.86 59 440 7924 6.59
Glass/ITO/ZnO/PCDTBT:PC70BM/MoO3/Ag_Device_2 0.98 13.51 56 686 5660 7.43
Glass/ITO/ZnO/PCDTBT:PC70BM/MoO3/Ag_Device_3 1.01 12.54 53 201 7204 6.66

stable, with their PCEs remaining unchanged after being stored in Acknowledgements
the air for several days. In order to obtain more efficiency from The facilities provided by the Photonics Research Laboratory, School
multilayer inverted OSCs, further investigation must be carried of Studies in Electronics and Photonics, Pt. Ravishankar Shukla
out to enhance the overall performance of the devices based on University, Raipur, Chhattisgarh, India, are acknowledged. The
novel materials. fabrication and characterization facilities provided by the Indian

6
Downloaded by [ University of Melbourne] on [31/10/20]. Copyright © ICE Publishing, all rights reserved.
 Nanomaterials and Energy Effect of ZnO ETL and MoO3 HTL with
PCDTBT:PC70BM-based BHJ organic
solar cells
Verma, Shukla and Tiwari

Table 4. Comparison between this work and some other novel work reported in the literature
Device structure ETL/active layers/HTL Voc: V Jsc: mA/cm2 FF: % g: % Reference
Pedot:PSS/PCDTBT:PC70BM/MoOx 0.89 18.88 67 6.50 Sun et al.39
PCDTBT:PC70BM/titanium dioxide 0.88 10.59 63 5.96 Park et al.21
PCDTBT:PCBM with silver NPs 0.84 4.64 44 1.72 Parlak et al.45
Zinc oxide/PCDTBT:PC70BM/molybdenum trioxide 0.98 13.51 56 7.43 This work

Institute of Technology, Bombay, under an Indian Nanoelectronics 15. Yu G, Gao J, Hummelen JC, Wudl F and Heeger AJ (1995) Polymer
User Program-funded program, which is supported by the photovoltaic cells: enhanced efficiencies via a network of internal
Department of Electronics and Information Technology, Ministry of donor-acceptor heterojunctions. Science 270(5243): 1789–1791.
16. Sariciftci NS, Smilowitz L, Heeger AJ and Wudl F (1992) Photoinduced
Communication and Information Technology, Government of India, electron transfer from a conducting polymer to buckminsterfullerene.
is very much acknowledged. Science 258(5087): 1474–1476.
17. Blom PW, Mihailetchi VD, Koster LJ and Markov DE (2007) Device
REFERENCES physics of polymer: fullerene bulk heterojunction solar cells.
1. Brabec CJ, Sariciftci NS and Hummelen JC (2001) Plastic solar cells. Advanced Materials 19(12): 1551–1566.
Advanced Functional Materials 11(1): 15–26. 18. Günes S, Neugebauer H and Sariciftci NS (2007) Conjugated polymer-
2. Verma AK, Agnihotri P, Patel M, Sahu S and Tiwari S (2017) Recent based organic solar cells. Chemical Reviews 107(4): 1324–1338.
advances in polymer solar cells. In Recent Advances in Photovoltaics 19. Dennler G, Scharber MC and Brabec CJ (2009) Polymer–fullerene bulk-
(Ramrakhiani M (ed.)). Materials Research Forum LLC, Millersville, heterojunction solar cells. Advanced Materials 21(13): 1323–1338.
PA, USA, pp. 299–309. 20. Chen LM, Hong Z, Li G and Yang Y (2009) Recent progress in
3. Görrn P, Sander M, Meyer J et al. (2006) Towards see-through polymer solar cells: manipulation of polymer: fullerene morphology
displays: fully transparent thin-film transistors driving transparent and the formation of efficient inverted polymer solar cells. Advanced
organic light-emitting diodes. Advanced Materials 18(6): 738–741. Materials 21(14–15): 1434–1449.
4. Shrotriya V, Wu EH, Li G, Yao Y and Yang Y (2006) Efficient light 21. Park SH, Roy A, Beaupré S et al. (2009) Bulk heterojunction solar
harvesting in multiple-device stacked structure for polymer solar cells. cells with internal quantum efficiency approaching 100%. Nature
Applied Physics Letters 88(6): article 064104. Photonics 3(5): 297–302.
5. Oyamada T, Sugawara Y, Terao Y, Sasabe H and Adachi C (2007) 22. Blouin N, Michaud A, Gendron D et al. (2008) Toward a rational
Top light-harvesting organic solar cell using ultrathin Ag/MgAg layer design of poly(2,7-carbazole) derivatives for solar cells. Journal of the
as anode. Japanese Journal of Applied Physics 46(4R): article 1734. American Chemical Society 130(2): 732–742.
6. Li G, Chu CW, Shrotriya V, Huang J and Yang Y (2006) Efficient inverted 23. Wang E, Hou L, Wang Z et al. (2010) An easily synthesized blue
polymer solar cells. Applied Physics Letters 88(25): article 253503. polymer for high-performance polymer solar cells. Advanced
7. Hau SK, Yip HL and Jen AK (2010) A review on the development of Materials 22(46): 5240–5244.
the inverted polymer solar cell architecture. Polymer Reviews 50(4): 24. Liang Y, Xu Z, Xia J et al. (2010) For the bright future – bulk
474–510. heterojunction polymer solar cells with power conversion efficiency
8. Kyaw AK, Sun XW, Jiang CY et al. (2008) An inverted organic solar of 7.4%. Advanced Materials 22(20): E135–E138.
cell employing a sol–gel derived ZnO electron selective layer and 25. Zhou H, Yang L, Price SC, Knight KJ and You W (2010) Enhanced
thermal evaporated MoO3 hole selective layer. Applied Physics photovoltaic performance of low-bandgap polymers with deep LUMO
Letters 93(22): article 221107. levels. Angewandte Chemie International Edition 122(43): 8164–8167.
9. Brabec CJ, Gowrisanker S, Halls JJ et al. (2010) Polymer–fullerene 26. Chen YC, Yu CY, Fan YL et al. (2010) Low-bandgap conjugated
bulk-heterojunction solar cells. Advanced Materials 22(34): polymer for high efficient photovoltaic applications. Chemical
3839–3856. Communications 46(35): 6503–6505.
10. Chen S, Manders JR, Tsang SW and So F (2012) Metal oxides for 27. Chen LM, Xu Z, Hong Z and Yang Y (2010) Interface investigation
interface engineering in polymer solar cells. Journal of Materials and engineering – achieving high performance polymer photovoltaic
Chemistry 22(46): 24202–24212. devices. Journal of Materials Chemistry 20(13): 2575–2598.
11. Ma Z, Tang Z, Wang E et al. (2012) Influences of surface roughness 28. Steim R, Kogler FR and Brabec CJ (2010) Interface materials for organic
of ZnO electron transport layer on the photovoltaic performance of solar cells. Journal of Materials Chemistry 20(13): 2499–2512.
organic inverted solar cells. Journal of Physical Chemistry C 116(46): 29. Kim JY, Lee K, Coates NE et al. (2007) Efficient tandem polymer solar
24462–24468. cells fabricated by all-solution processing. Science 317(5835): 222–225.
12. Zhu F, Chen X, Zhou L et al. (2014) Dependence of the performance 30. Wang DH, Im SH, Lee HK, Park OO and Park JH (2009) Enhanced
of inverted polymer solar cells on thickness of an electron selective high-temperature long-term stability of polymer solar cells with a
ZnO layer deposited by magnetron sputtering. Thin Solid Films 551: thermally stable TiOx interlayer. Journal of Physical Chemistry C
131–135. 113(39): 17268–17273.
13. Verma AK, Agnihotri P, Patel M, Sahu S and Tiwari S (2016) 31. Gao D, Helander MG, Wang ZB et al. (2010) C60:LiF blocking layer
Fabrication and characterization of novel inverted organic solar cells for environmentally stable bulk heterojunction solar cells. Advanced
employing ZnO ETL and MoO3 HTL. Proceedings of the 13th Materials 22(47): 5404–5408.
International Conference on Fibre Optics and Photonics, Kanpur, 32. Cheng F, Fang G, Fan X et al. (2011) Enhancing the short-circuit
India, paper no. Tu4A-18. current and efficiency of organic solar cells using MoO3 and CuPc as
14. Tiwari S, Yakhmi JV, Carter S and Scott JC (2018) Optimization of buffer layers. Solar Energy Materials and Solar Cells 95(10):
bulk heterojunction organic photovoltaic devices. In Handbook of 2914–2919.
Ecomaterials (Martínez L, Kharissova O and Kharisov B (eds)). 33. Litzov I and Brabec CJ (2013) Development of efficient and stable
Springer, Cham, Switzerland, https://doi.org/10.1007/978-3-319- inverted bulk heterojunction (BHJ) solar cells using different metal
48281-1_66-1. oxide interfaces. Materials 6(12): 5796–5820.

7
Downloaded by [ University of Melbourne] on [31/10/20]. Copyright © ICE Publishing, all rights reserved.
 Nanomaterials and Energy Effect of ZnO ETL and MoO3 HTL with
PCDTBT:PC70BM-based BHJ organic
solar cells
Verma, Shukla and Tiwari

34. Thambidurai M, Kim JY, Kang CM et al. (2014) Enhanced 40. O’Brien S, Koh LH and Crean GM (2008) ZnO thin films prepared by
photovoltaic performance of inverted organic solar cells with In-doped a single step sol–gel process. Thin Solid Films 516(7): 1391–1395.
ZnO as an electron extraction layer. Renewable Energy 66: 433–442. 41. Sun Y, Seo JH, Takacs CJ, Seifter J and Heeger AJ (2011) Inverted
35. Zhang Y, Bovill E, Kingsley J et al. (2016) PCDTBT based solar cells: polymer solar cells integrated with a low-temperature-annealed
one year of operation under real-world conditions. Scientific Reports sol–gel-derived ZnO film as an electron transport layer. Advanced
6: article 21632. Materials 23(14): 1679–1683.
36. Kim JY, Kim SH, Lee HH et al. (2006) New architecture for high- 42. Kim J, Kim G, Kim TK et al. (2014) Efficient planar-heterojunction
efficiency polymer photovoltaic cells using solution-based titanium perovskite solar cells achieved via interfacial modification of a sol–gel
oxide as an optical spacer. Advanced Materials 18(5): 572–576. ZnO electron collection layer. Journal of Materials Chemistry A
37. Roy A, Park SH, Cowan S et al. (2009) Titanium suboxide as an 2(41): 17291–17296.
optical spacer in polymer solar cells. Applied Physics Letters 95(1): 43. Horcas I, Fernández R, Gomez-Rodriguez JM et al. (2007) WSXM:
article 013302. software for scanning probe microscopy and a tool for nanotechnology.
38. Bagui A, Garg A, Tyagi B, Gupta V and Singh SP (2018) A fluorene- Review of Scientific Instruments 78(1): article 013705.
core-based electron acceptor for fullerene-free BHJ organic solar 44. Yuan T, Zhu X, Zhou L, Zhang J and Tu G (2015) Efficient inverted
cells – towards power conversion efficiencies over 10%. Chemical polymer solar cells based on conjugated polyelectrolyte and zinc oxide
Communications 54(32): 4001–4004. modified ITO electrode. Applied Physics Letters 106(8): article 083302.
39. Sun Y, Takacs CJ, Cowan SR et al. (2011) Efficient, air-stable bulk 45. Parlak EA, Tumay TA, Tore N et al. (2013) Efficiency improvement of
heterojunction polymer solar cells using MoOx as the anode interfacial PCDTBT solar cells with silver nanoparticles. Solar Energy Materials
layer. Advanced Materials 23(19): 2226–2230. and Solar Cells 110: 58–62.

How can you contribute?

To discuss this paper, please submit up to 500 words to the
journal office at [email protected]. Your contribution will
be forwarded to the author(s) for a reply and, if considered
appropriate by the editor-in-chief, it will be published as a
discussion in a future issue of the journal.

ICE Science journals rely entirely on contributions from

the field of materials science and engineering. Information
about how to submit your paper online is available at
www.icevirtuallibrary.com/page/authors, where you will also
find detailed author guidelines.

8
Downloaded by [ University of Melbourne] on [31/10/20]. Copyright © ICE Publishing, all rights reserved.