Materials Science in Semiconductor Processing 93 (2019) 215–225

Contents lists available at ScienceDirect

Materials Science in Semiconductor Processing

journal homepage: www.elsevier.com/locate/mssp

Band gap tuning and applications of ZnO nanorods in hybrid solar cell: Ag- T
doped verses Nd-doped ZnO nanorods
⁎
Abdus Saboor, Syed Mujtaba Shah , Hazrat Hussain
Department of Chemistry, Quaid-i-Azam University, Islamabad 45320, Pakistan

A R T I C LE I N FO A B S T R A C T

Keywords: ZnO nanorods doped with different concentrations of Ag and Nd (1–7%) were synthesized by hydrothermal
Doping method. In this article we describe the synthesis, characterization and applications of pristine ZnO, Ag-doped
Band gap tuning ZnO and Nd-doped ZnO nanorods in hybrid bulk heterojunction solar cells. Their optical, structural, and mor-
Bromopyrogallol red dye (Br-PGR) phological properties were analyzed by using UV–Visible spectroscopy, X-ray diffraction (XRD), Scanning
Charge transfer complex
electron microscopy (SEM), and Energy dispersive X-ray spectroscopy (EDX). The X-ray diffraction analysis
Chemisorption
Dye sensitized solar cells
reveals that the pristine and doped ZnO nanorods were crystallized in a hexagonal wurtzite structure. SEM
images supplemented with EDX were used to explore the morphology, size and chemical composition of pristine
ZnO, Ag-doped ZnO and Nd-doped ZnO samples. UV visible absorption spectra showed that bathochromic shift
occurred when ZnO nanorods were doped with Ag and Nd up to a certain limit of dopant concentration. Doped
ZnO nanorods were found more conducting than prisitne ZnO nanorods. This work also represents the chemical
modification of pristine ZnO, Ag-doped ZnO, and Nd-doped ZnO nanorods with a bromopyrogallol red dye (Br-
PGR) which is not reported yet. The pristine and doped samples were sensitized with Br-PGR and the material so
sensitized was tested in solar cell. The optical properties of grafted samples were thoroughly studied by using
UV–visible spectroscopy. The Nano-hybrid material was tested as a photoactive blend of the DSSCs and their
current-voltage measurements (I-V) were performed to examine the effect of pristine and doped ZnO nanorods
on the performance of solar cells. Moreover current voltage (I-V) measurements confirmed the boosting of ef-
ficiency in pristine and doped ZnO nanorods based DSSCs owing to their sensitization with Br-PGR. Maximum
power conversion efficiency of 1% was recorded for Ag-doped ZnO nanorods.

1. Introduction that absorb the solar light to energize electrons and insert them into the
conduction band of wide band gap metal oxides and (iii) open-circuit
In the course of recent years, Organic-based photovoltaic devices voltage and non-corrosive redox mediator with improved dye re-
have pulled marvelous attention as next generation solar cells because generation [4,5]. After the remarkable work presented by Grätzel and
of their light weight, great solution processability, inexpensive and O’Regan in 1991, the maximal power conversion efficiency (PCE)
large scale fabrication [1,2]. The concept of dye sensitized solar cell is achieved for DSSCs within the last two decades is 13% [6,7]. Never-
commonly based on the photoexcitation of a sensitizer which in- theless, devices still experience generally low efficiency and poor sta-
troduces an electron (e-) into the conduction band of a nanostructured bility in comparison with dominant silicon based solar cells. Many re-
metal oxide having wide band gap. The oxidized dye molecule is sub- search groups and associations have tried new endeavors to further
sequently regenerated back by capturing an electron from a redox enhance the performance and stability of DSSCs.
couple in an electrolyte surrounding sensitized semiconducting mate- One approach to boost the efficiency of DSSCs is to thoroughly study
rial. Light harvesting and transport of charge carriers are therefore se- the structure and chemical nature of dye. A wide variety of inorganic
parated by a proper combination of these three materials: electrolyte, dyes and organic dyes are used as photosensitizers [8–14]. The dye
metal oxide and dye [3]. The extraordinary performance of these cells must contain an anchoring group such as a carboxyl group (COOH)
essentially rely upon the advancement or improvement of the key which helps in forming a chemical bond between the metal oxide sur-
constituents – (i) semiconducting nanomaterials having character- face and the dye molecule. For quite a long while, TiO2 nanostructured
istically effective charge transfer properties, (ii) photosensitizing dyes materials and the ruthenium-bipyridyl dye groups, for example, C101,

⁎
Corresponding author.
E-mail address: s.mujtaba@qau.edu.pk (S.M. Shah).

https://doi.org/10.1016/j.mssp.2019.01.009
Received 11 September 2018; Received in revised form 14 December 2018; Accepted 7 January 2019
1369-8001/ © 2019 Elsevier Ltd. All rights reserved.
A. Saboor et al. Materials Science in Semiconductor Processing 93 (2019) 215–225

Scheme 1. Chemical structures of (a) Bromopyrogallol Red Dye, (b) 3-dimentional structure of Bromopyrogallol Red Dye and (c) Poly(3-hexylthiophene). (For
interpretation of the references to color in this figure legend, the reader is referred to the web version of this article.)

less efficient than conventional DSSCs based on liquid electrolyte [21].

Semi-conducting metal oxides such as TiO2, SnO2, Nb2O5, and ZnO
being used as photoanode materials for DSSC photoelectrodes [22–26].
Among these semiconductors, ZnO nanostructures have attracted much
more attention because its optical bandgap is comparable to that of
TiO2 and it is considered as an eminent substitute of TiO2 due to its ease
of anisotropic growth and crystallization. ZnO, an important group II-VI
compound, n-type semiconductor having hexagonal wurtzite structure
and a wide direct bandgap of 3.37 eV at room temperature has many
distinct properties, for example, excellent electronic properties, high
electrochemical stability, acoustic characteristics, high infrared re-
flectivity, and transparency in the visible region. It has large number of
applications in sunlight harvesting, piezoelectric, sensors, optoelec-
tronic devices and spintronics [27,28]. Borgohain et al. synthesized
Fig. 1. Energy level diagram showing the LUMO/HOMO levels of the compo-
ZnO nanorods on an array of interdigitated electrodes and employed
nents of photoactive blend.
them in UV detectors [29]. Yu et al. synthesized Fe-doped ZnO porous
nanosheets by hydrothermal method and used them as gas sensor de-
N3 and N719 are regarded as the most encouraging materials for vices [30]. Various endeavors have been made to apply ZnO nanos-
photoanode. For instance, TiO2-based solar cell sensitized with N719 tructures in photoelectrochemical solar cells. It has been observed that
has a global conversion efficiency of more than 10% [15,16]. The Swiss ZnO-based nanostructures, specially in the form of nanorods/nanowires
Federal Institute of Technology in Lausanne (EPFL) has reported the arrays, have excellent applications in DSSC's [31]. In early 1969, Ger-
conversion efficiency of DSSCs up to 10.4% by using black dye as a ischer produced dye-sensitized semiconducting single-crystal ZnO
photosensitizer [17]. Recently, DSSCs with a record efficiency(η %) of electrodes [32]. When these ZnO nanostructures were used as the
12.3% was found for a liquid redox electrolyte containing one-electron photoelectrodes, a remarkable enhancement in the performance of solar
cobalt-complex redox mediators [18,19]. However, to eliminate most cell was noticed. This was ascribed to its potential of providing direct
problems of fabrication and production life time, it is imperative to transport pathways for the photoexcited electrons, effective light-har-
replace liquid electrolytes with noncorrosive and nonvolatile materials vesting efficiency and large surface area for the adsorption of dye [33].
[20]. To resolve these issues, scientists emphasize on producing solid The photovoltaic performance of ZnO NRs-P3HT devices suffers from
state and more reliable substitute in the form of hybrid bulk hetero- charge recombination and trapping, which are mostly assigned to the
junction solar cells. The solid-state DSSCs (ssDSCs) are more stable and existence of intrinsic surface defective states and unfavourable

216
A. Saboor et al. Materials Science in Semiconductor Processing 93 (2019) 215–225

Fig. 2. (a) Absorbance spectra of pristine ZnO nanorods (solid). ZnO doped with 1% Ag (short dot), 3% Ag (short dash dot), 5% Ag (dash dot) and 7% Ag (short dash).
(b) Absorbance spectra 1% (short dot) and 5% (short dash) Nd-doped ZnO.

Fig. 3. Tauc plots for (a) ZnO (solid line), (b) Ag-doped ZnO, 1% (short dot), 3% (short dash) (c) Ag-doped ZnO, 5% (short dash), 7% (solid) (d) Nd-doped ZnO, 1%
(short dot), 5% (short dash).

morphology (interfacial area) [34]. Therefore, more attention has been ZnO with arsenic and phosphorus for controling P-type conductivity has
concentrated on improving the photovoltaic performance through op- also been reported [43,44]. Zamiri et al. examined the influence of rare-
timization of nanorod morphology, surface treatment via acoustic vi- earth dopants (Er, La and Yb) on the morphology and optical band gap
bration, surface modification, and self-assembled monolayers [35–39]. of the as synthesized ZnO nanostructures [45]. Oleg Lupan et al. in-
Nonetheless, the aforementioned methods require some additional vestigated the impacts of Ag and Sb dopants on the chemical, structural,
steps of chemical modification and external treatment. Recently, in- optical properties and vibrational modes of ZnO nanorods prepared by
corporation of metal cations into the crystal lattice of ZnO nanorods has facile hydrothermal technique [46]. Thierry Pauporté et al. have ex-
resulted in hopeful outcomes; not only in the sense of controlling the plained the low temperature synthesis of Ag-doped ZnO nanowires,
morphology but also suppressing the oxygen defects [40–42]. Doping of their DFT Studies and its applications in light emitting diodes [47].

217
A. Saboor et al. Materials Science in Semiconductor Processing 93 (2019) 215–225

Table 1 Table 2
Optical band gap of Ag and Nd-doped ZnO nanorods at different dopant con- Parameters Obtained for the (100) and (002) Diffraction Peaks.
centration.
Sample Description (hkl) planes 2θ (deg) [fwhm] (deg)
Dopant content Parameters
#1 ZnO (100) 31.74 0.39
λmax nm Band gap (eV) (002) 34.42 0.19
#2 Ag-ZnO (0.01) (100) 31.79 0.17
Ag content (002) 34.40 0.098
0.0 362.5 3.27 0.03 (100) 31.83 0.13
0.01 371.5 2.95 (002) 34.50 0.098
0.03 378 2.64 0.05 (100) 31.77 0.15
0.05 375 2.80 (002) 34.44 0.17
0.07 368.5 3.08 0.07 (100) 31.74 0.078
Nd content (002) 34.41 0.059
0.0 362.5 3.27 #3 Nd-ZnO (0.01) (100) 31.75 0.13
0.01 370.5 3.01 (002) 34.40 0.11
0.03 373.5 2.97 0.03 (100) 31.80 0.11
0.05 376 2.94 (002) 34.49 0.11
0.07 378.5 2.65 0.05 (100) 31.78 0.098
(002) 34.42 0.11
0.07 (100) 31.80 0.11
(002) 34.49 0.098

Br-PGR, which resulted in improving the charge transfer from the

polymer to metal oxide. In this context, Ag and Nd impurities were
successfully incorporated into the crystal lattice of ZnO nanorods
during hydrothermal growth. Ag and Nd incorporation is highly effec-
tive to enhance the conversion efficiency of hybrid polymer/metal
oxide solar cells fabricated from poly(3-hexylthiophene) (P3HT) as the
donor and ZnO nanorods as the electron transporting layer. The results
showed that morphology, structure, and intrinsic defects of ZnO na-
norods were highly dependent on the Ag and Nd doping concentration
as it shifts the conduction band and Fermi level of ZnO nanorods. It was
found that doping of Ag and Nd into ZnO can simultaneously enhance
Fig. 4. X-ray diffraction patterns of pristine ZnO and Ag-doped ZnO (1–7%) the short circuit current density (Jsc) and open circuit voltage (Voc) due
(Bottom to top). The peaks marked with (*) represent the signals of Ag and the
to the suppression of oxygen defects, increase of charge carrier mobi-
remaining peaks represent the signals from ZnO.
lity, and efficient exciton dissociation, but the efficiency was found
more for Ag-doped ZnO nanorods than pristine ZnO and Nd-doped ZnO
nanorods. Pristine ZnO, Ag-doped ZnO and Nd-doped ZnO nanorods
were prepared by hydrothermal procedure and the effects of Ag and Nd
dopants on the photovoltaic performance of DSSC's were thoroughly
investigated.

2. Experimental methods

2.1. Chemicals used

Analytical grade Zinc acetate (Zn (CH3COO)2·2H2O) and Sodium

Hydroxide (NaOH) were purchased from Sigma Aldrich and were used
to synthesize ZnO nanorods. Silver Chloride (AgCl) and Neodymium
Oxide (Nd2O3) were used as precursors for doping. Absolute methanol
Fig. 5. X-ray diffraction patterns of pristine ZnO and Nd-doped ZnO (1–7 wt%) (CH3OH), Deionized water, Ethylene Glycol (C2H6O2), and Ammonium
(Bottom to top). Hydroxide (NH4OH) were used as medium for the synthesis without
further purification.
Yongsheng Liu et al. used facile sol-gel method for the synthesis of
Nd3+-doped ZnO nanocrystals with multiple luminescent centers and 2.2. Synthesis of ZnO and M-ZnO nanorods
studied their photoluminescence (PL), PL excitation, and ZnO-to-Nd3+
energy transfer in ZnO nanocrystals in detail [48]. Fenglin Xian et al. ZnO nanorods were synthesized by facile hydrothermal procedure
synthesized thin films of Nd-doped ZnO on glass substrates with 1%, 3% with a little modification [51]. Two main processes are involved in the
and 5% Nd doping levels by using sol–gel technique and their optical synthesis of ZnO samples: (i) sol–gel process, 4.38 g of zinc acetate (Zn
measurements demonstrated that the absorption peak was shifted to (CH3COO)2·2H2O) was dissolved in 24 ml of deionized water. Then
shorter wavelength with increasing dopant concentration [49]. 10 ml of NaOH (7 M) was added drop wise to the aqueous solution of
Most of the hybrid bulk heterojunction solar cells show less pho- zinc acetate under continuous magnetic stirring for 30 min at 50 °C. A
tovoltaic performance because of the large band offset between the milky solution was obtained. To this milky solution 15 ml of ammonium
electron donor and electron acceptor materials and also due to lack of hydroxide was added drop wise and stirred for 30 min at 50 °C. Finally
efficient charge generation and charge transport at their interface [50]. 10 ml of ethylene glycol was added to the as prepared reaction mixture
In this work, we introduce for the first time, the surface modification of and was stirred for 10 min to form a gel. (ii) Hydrothermal process, The
the semiconductor (pristine ZnO, Ag-doped ZnO and Nd-doped ZnO) by gel obtained from the previous step was transferred to 120 ml Teflon-

218
A. Saboor et al. Materials Science in Semiconductor Processing 93 (2019) 215–225

Fig. 6. SEM micrographs of (a) (b) pristine ZnO, (c) (d) Ag-doped ZnO and (e) (f) Nd-doped ZnO.

lined stainless autoclave and was placed in furnace for 12 h at 150 °C colored grafted precipitate settled down at the bottom and a slightly
followed by cooling it to room temperature. A white solid precipitate of light colour liquid remained at the top. This mixture was centrifuged
pure ZnO nanorods was formed which was centrifuged washed 4 times and thoroughly washed two times with distilled methanol and was
with methanol. The resultant white precipitate was then calcined at placed in dark for drying. During the grafting process, the solvent used
300 °C for 3 h. The same method was used to synthesize 1%, 3%, 5%, was distilled methanol. The grafted materials after proper dilution were
and 7% M-ZnO (M-Ag and Nd) but the only difference was that after subjected to optical and morphological investigations.
adding NaOH to the aqeous solution of zinc acetate and formation of
the milky solutions, metal precursor was added (1–7 wt% of zinc 2.4. Device fabrication and current voltage (I-V) measurements
acetate). For doping of ZnO, the concentration of Zinc acetate was
regulated according to the concentration of dopant i.e. the quantity of ITO coated glass was washed and cleaned with isopropyl alcohol
zinc acetate used for the synthesis of pure ZnO and the quantity of and acetone. It was used as substrate for solar cell. The solar cells were
dopant (in grams) were subtracted from one another. For 1% dopant, fabricated according to a procedure already reported [52,53]. A fine
the amount of ZnO (in grams) was multiplied by 0.01 (1%) which gives sheet of PEDOT-PSS [Poly(3,4-ethylenedioxythiophene)] polystyrene
the amount of dopant to be added. The amount of zinc acetate was then sulphonate was deposited on the top of substrate in the form of a thin
reduced by 1% thnn that used for the synthesis of pure ZnO. For all layer. Graphene composites and dye grafted nanoparticles mixed with
other dopant concentrations, the same procedure was repeated. Cal- 25 mg/ml of poly(3-hexylthiophene) (P3HT) solution in distilled me-
culations for 1% dopant are given below; thanol was used to prepare the active blend. This active blend was spin
4.38g(Zinc acetate) × 0.01 = 0.0438 g of dopant coated by keeping the spin coater at the acceleration of 1600 ms-2 and
at the speed of 18000 rpm. One more spin was given at 600 rpm for the
4.38 − 0.0438 = 4.33 grams of zinc acetate removal of any residue of the solvent. These slides were subsequently
annealed for 25 min at 100 °C. This annealing was done for improving
the surface morphology. Pt-coated glass was employed as a counter
2.3. Functionalization of pristine ZnO, Ag-ZnO and Nd-ZnO nanorods with electrode in order to complete a circuit. Current-voltage measurements
bromopyrogallol red dye (Br-PGR) were carried out by using solar simulator along with a tungsten halogen
lamp (150 W) and AM1.5 G (Oriel 81086 filter) in the presence of air.
Br-PGR was chemisorbed over the surface of pristine ZnO, Ag-doped Keithly model 2400 source meter was employed for I-V measurements.
ZnO and Nd-doped ZnO nanorods in 7 mM dye concentration. 1 mg/ml
solution of the pristine/doped ZnO nanorods was added to 1.5 ml so- 2.5. Characterization of samples
lution of dye. This mixture of dye and ZnO nanorods were kept stirring
for 3 h in order to make an effective contact between dye and ZnO Following techniques have been employed as a part of this work for
nanorods. After 3 h, stirring was stopped and it was noticed that the characterization of prepared materials. UV–visible (Shimadzu 1601

219
A. Saboor et al. Materials Science in Semiconductor Processing 93 (2019) 215–225

Fig. 7. EDX images of (a) Pure ZnO (b) Ag-doped ZnO and (c) Nd-doped ZnO nanorods.

spectrophotometer) was used to study the optical absorption properties which includes
of pristine ZnO, Ag-ZnO and Nd-ZnO nanorods, photosensitizers, and
Nano-hybrid samples. X-ray diffraction (XRD) was taken on an Xpert • ZnO as an inorganic semiconductor,
Pro Philips powder X-beam diffractometer. Field emission gun scanning • P3HT as an organic semiconductor and hole transporting medium
electron magnifying instrument (FESEM; MIRA3 TESCAN) appended • Bromopyrogallol red dye as a photo-sensitizer.
with EDX was used to observe the morphology, chemical composition
and size of nanorods. I-V measurements were made for fabricated solar Scheme 1 represents the chemical structure of Br-PGR and poly(3-
cells which were performed by using AM 1.5 G (Oriel 81,086) filter and hexylthiophene).
a tungsten halogen lamp (150 W, light power density 100 mW/cm2) in Density functional theory (DFT) calculations were performed for Br-
the presence of air. Current-voltage (I-V) measurements were made by PGR by using Gaussian 09W program, to have an idea of feasibility of
using Source Meter (Keithley Model 2400). The monocrystalline silicon directional drift of charges in the nanohybrid assembly, from P3HT to
solar cell was employed for the calibration of light intensity. the Br-PGR dye and then towards the conduction band of ZnO. The
HOMO-LUMO energies of materials were calculated by using Gaussian
09W program with DFT/B3LYP method having 6–31G (d) basis set in
3. Results and discussion
the ground state. The LUMO level of Br-PGR lies higher than the con-
duction band of ZnO. This cascade favors the flow of charges very well
The photoactive nano-hybrid material consists of three components

220
A. Saboor et al. Materials Science in Semiconductor Processing 93 (2019) 215–225

Fig. 10. Energy levels of the ZnO Ag-doped ZnO and Nd-doped ZnO photo-
anodes. The valence band maximum (VBM; red colour) and the conduction
band minimum (CBM; blue colour) are expressed in eV. The ground (HOMO;
Fig. 8. UV–visible absorption spectra of pure dye (solid), ZnO-Br-PGR (dash), red) and excited states (LUMO; blue) of Br-PGR dye is also shown. The energy
Ag-doped Zno-Br-PGR (small dots) and Nd-doped ZnO-Br-PGR (dot dash). scale is referenced to the vacuum level. (For interpretation of the references to
color in this figure legend, the reader is referred to the web version of this
article.).

impurity generates an energy state in the energy gap near the con-
duction band edge and a shallow acceptor impurity generates an energy
state near the valence band edge. By increasing the concentration of
dopant, the density of energy levels increases which results in forming a
continuum of energy levels. This leads to the reduction of optical band
gap [55,56]. Moreover, the interaction of Nd and Ag energy states with
the host (ZnO states) leads to the formation of energy states in the
optical band gap which results in the reduction of the band gap of ZnO
[62].
But when concentration of Ag dopant was increasesd to 5% and 7%,
the absorption spectra of Ag-doped ZnO nanorods underwent blue shifts
which are centered at 375 and 368.5 nm respectively. The blue shift is
an indication of increase in the band gap, which is generally ascribed to
the strong chemical interaction between the surface oxides of Ag and Zn
Fig. 9. Current-voltage (I-V) curves of reference cell, P3HT-ZnO dark (solid),
as well as the quantum size effect. This blue shift in the optical ab-
P3HT-ZnO light (short dot), P3HT-ZnO-Br-PGR (dash dot), P3HT-Ag-ZnO-Br-
sorption spectra at dopant concentration higher than 3% was described
PGR (short dash) and P3HT-Nd-ZnO-Br-PGR (dash), ZnO nanorods based solar
cells. by the Burstein–Moss effect. According to Burstein–Moss effect, when
the concentration of dopant is increased beyond a certain limit, It leads
to increase in the concentration of charge carriers. Consequently the
towards the cathode which is represented in Fig. 1. Fermi level which lies just below the conduction band of semiconductor
is fully filled. Thereafter the extra excited electrons enter into the
3.1. Optical studies and bandgap tuning conduction band. This scenario results in increasing the energy gap of
the semiconductor and thus a blue shift is observed in the absorption
The optical absorption spectra of pristine ZnO, Ag-doped ZnO and spectra of ZnO [57,58].
Nd-doped ZnO nanorods were used to investigate their light absorption Absorption spectroscopy was then performed for 1–7% Nd-doped
properties. Fig. 2a and b represents the absorption spectra of pristine ZnO nanorods as shown in Fig. 2b. It presents that all the Nd-doped ZnO
ZnO, Ag-doped ZnO and Nd-doped ZnO nanorods with the amount of nanorods show strong absorbance in the ultraviolet region. By in-
dopant x ranging from x = 0.0–0.07, respectively. The strong absorp- creasing the concentration of Nd dopant, the absorption steadily in-
tion peak of ZnO nanorods at 362.5 nm might be assigned to hexagonal creases. It is clear that as the amount of dopant increases, the absor-
wurtzite crystal structure of ZnO [54]. With addition of 1% and 3% bance peaks of doped samples moves towards longer wavelength. This
silver to ZnO nanorods, the absorption peak was shifted towards longer red shift was noticed for all Nd-doped ZnO samples. This shift indicates
wavelengths (red shift) and appeared at 371.5 and 378 nm respectively. the narrowing of the band gap which originates due to the charge
Changes in the position of absorption could be assigned to changes in transfer between the valance band of ZnO and the 4f energy state of
the band structure. Band gap narrowing as a result of doping is the most rare earth ion [59]. Literature has revealed different effects on the band
common phenomenon in all semiconducting materials. A shallow donor

Table 3
Characteristic parameters of solar cells composed of pure ZnO, dye grafted pristine ZnO, Ag-doped ZnO and Nd-doped ZnO, calculated from current-voltage plots.
JSC (mA/cm2) VOC (V) MPP (mW/cm2) Fill factor Efficiency (η%)

P3HT-ZnO 2.3 0.42 0.966 0.45 0.43

P3HT-ZnO-Br-PGR (7 × 10-3) 5.8 0.36 2.088 0.39 0.814
P3HT-Ag-ZnO-Br-PGR (7 × 10-3) 6.77 0.40 2.708 0.37 1
P3HT-Nd-ZnO-Br-PGR (7 × 10-3) 5.22 0.40 2.088 0.36 0.75

221
A. Saboor et al. Materials Science in Semiconductor Processing 93 (2019) 215–225

gap of ZnO doped with Neodymium. For instance, Zhou et al. synthe- Where θ is the scattering angle in degrees, β is full width at half max-
sized Nd-doped ZnO nanoparticles through sol–gel method by using imum [FWHM] in radian, λ is wavelength of X-ray in A° and D is the
different concentrations of Nd and he found that by increasing dopant crystallite size in nm.
concentration band gap was increased [60]. But Liu et al. found that by The X-ray diffraction pattern of Nd-doped ZnO nanorods are dis-
using different concentration of Nd, the optical band gap of ZnO na- played in Fig. 5. All diffraction peaks of the doped samples matches well
noparticles was decreased [61,62]. These contradictory reports might with the wurtzite hexagonal crystal structure. There were no additional
be associated with the changed annealing environment and tempera- peaks detected in the XRD pattern which corresponds to neodymium
ture. oxides or neodymium metal clusters. This specifies that Neodymium has
The optical bandgap was calculated using Tauc plot by plotting penetrated into the crystal lattice of ZnO without changing its crystal
(αhʋ)2 versus hʋ. Fig. 3 shows the Tauc plots used for the calculation of structure. At dopant level of 1%, (002) plane is intense and no extra
optical band gap of pristine ZnO, Ag-doped ZnO and Nd-doped ZnO peak exists, which means that at 1% Nd dopant concentration the
nanorods. Based on the calculations, the band gap energies of the doped crystalline behavior of ZnO nanorods is effectively enhanced. But when
samples were found lower than pristine ZnO nanorods and the results Nd doping level exceeds 1%, the peak intensity of (002) plane de-
are shown in Table 1. creases, this behavior shows that the substitution of Nd3+ ions inside
the crystal lattice of ZnO hinders the crystal growth of ZnO nanorods by
3.2. Structural characterization exerting stress on the growth [70]. Huang et al. reported the same re-
sults [71]. From the above results, it can be deduced that the crystal-
To examine the phase purity and crystallinity of the as synthesized linity of ZnO nanorods can be greatly enhanced by choosing a proper
ZnO nanorods, X-ray diffraction analysis was employed. Figs. 4 and 5 Nd-doping concentration. But when the concentration of dopant ex-
represent the XRD patterns of pristine ZnO, Ag-doped ZnO and Nd- ceeds 1%, the crystallization quality deteriorates. The averages crys-
doped ZnO nanorods, which illustrates that all the ZnO nanorods are talline size of Zn1-xNdxO nanorods (x = 0.01, 0.03, 0.05 and 0.07) were
crystallized in wurtzite structure [63]. found to be 72.68, 78.73, 83.53 and 83.57 nm respectively.
The XRD pattern of ZnO displayed in Fig. 4 reveals that peaks at 2θ and [fwhm] values taken from XRD patterns of Ag and Nd-doped
2θ = 31.74°, 34.42°, 36.25°, 47.47°, 56.64°, 62.81°, 66.35°, 67.97°, samples are listed in Table 2.
68.03°, and 69.06° were attributed to the (100), (002), (101), (102),
(110), (103), (200), (112) and (201) planes respectively, these are 3.3. SEM and EDX analyses
diffraction peaks of crystalline ZnO nanorods with a hexagonal wurtzite
structure (JCPDS Card No. 36-1451). However, in case of the Ag-doped SEM is considered as one of the most important technique for the
ZnO samples, a few extra peaks marked with “* ” are also formed which topographic study of the samples and it gives significant details re-
are associated to face-centered-cubic phase of metallic Ag (JCPDS file garding the size and shape of the nanorods. The surface morphology of
No. 04-0783) [64,65]. The presence of additional peaks in the XRD the ZnO, 7 at% Ag-doped ZnO and 7 at% Nd-doped ZnO nanorods are
patterns of Ag-doped ZnO reveals distinctly the formation of crystalline given in Fig. 6. The FE-SEM images clearly reveal the prominent growth
silver clusters in the nanorods. Comparing the diffraction pattern of in the diameter, size and change in the shape of the nanorods with the
pristine ZnO with Ag-doped ZnO, it was noticed that the diffraction doping of Ag and Nd. The SEM image of pure ZnO nanorods (Fig. 6a, b)
peaks of ZnO were not changed after silver anchoring, this indicates indicates the homogeneous distribution of nanorods over the surface
that Ag was not integrated into the ZnO crystal lattice. This could be having average particle size close to 131 nm and hexagonal shape. After
associated with considerably greater ionic radius of Ag1+ (126pm) than doping with Ag and Nd, the average diameter and size of nanorods
Zn2+ (74pm). Consequently, over the surface of ZnO a metallic phase of increases and the morphology gets irregular. The average size of Ag and
silver was formed. Furthermore it was detected that the intensity of Nd-doped ZnO lies within the range of 207 nm and 222 nm respectively.
diffraction peaks was first increased and then started decreasing with All samples have almost rod shaped morphology and undergo cluster-
increasing Ag concentration. The atomic radius of Ag1+ ion (1.22Å) is ization. The aspect ratio of Ag or Nd doped ZnO is lower, and size is
larger than the atomic radius of Zn2+ ion (0.72 Å), the increase in much bigger than pristine ZnO. This indicates that the doping of Ag and
number of Ag1+ ions in the lattice sites of Zn2+ ions contracts the Nd has decreased the aspect ratio of as-prepared ZnO nanorods. At high
lattice parameters [66]. It can also be seen very clearly that the FWHM dopant concentration (Ag and Nd), nanorods with larger diameter are
was decreased with increasing the amount of Ag impurity. The change grown; which can be attributed to formation of large number of Ag1+
in FWHM with Ag doping reveals that the crystallinity of nanorods and Nd3+ ions at high dopant level. As a result of this, complexes such
changes by changing the concentration of Ag dopant, which specifies as Zn(OH)4−x(OAg)2−x and Zn(OH)4−x(ONd)2−x are formed as the
that the huge number of silver atoms may enhance the preferential Ag1+ and Nd3+ ions stick to the Zn(OH) 42− growth units of the na-
growth of the nanorods along c-axis [67]. The same situation was also norods, and these complexes are then changed to Zn(OH)42−, that re-
noticed for copper doped ZnO films, where the advancement in the sults in increasing the growth rate [72,73]. SEM images of nanorods
crystallinity of sample was attributed to the moderate amount of Cu with irregular edges and hexagon side lengths have been shown in
atoms might exists at the interstitial sites and together with Zn atoms Fig. 6c, d, e and f. The latter shows that doping leads to considerable
share oxygen atoms [68]. effects on the morphology of ZnO nanorods.
To calculate the average crystalline size, (100) and (002) planes Chemical compositions of the pristine ZnO, Ag-doped ZnO and Nd-
were selected. Scherrer formula was used to determine the crystallite doped ZnO nanorods were analyzed by using energy dispersive X-ray
size which was found as 33.93 nm for ZnO and 69.70 nm, 77.54 nm, (EDX) spectroscopy (Fig. 7a, b and c). The EDX analysis confirmed that
57.33 nm and 128.96 nm for Zn1-xAgxO (x = 0.01, 0.03, 0.05 and 0.07) the sample is comprised of Zn and O elements with an average atomic
respectively [69]. This increment in the crystalline size of Ag-doped percentage ratio of 65.36:21.77 for pristine ZnO, and Zn, Ag and O
ZnO may be as a consequence of anchoring of some amount of Ag to the elements with average atomic percentage ratio of 63.89:4.73:23.49 for
surface of ZnO. The diffraction peak of Ag in (111) plane shown in 7 at% Ag-ZnO product while for 7 at% Nd-ZnO, the Zn, Nd and O ele-
Fig. 4 is comparatively weaker and broader, which indicates that silver ment present in average atomic percentage ratio of 60.74:6.72:24.83.
is well dispersed on the surface of ZnO. During EDX analysis, Cu mesh is used due to which peak of copper
The crystalline size of pristine ZnO, Ag-doped ZnO and Nd-doped arises while the carbon peak corresponds to paper strip used during
ZnO nanorods was calculated using the Scherrer equation: analysis. No other elemental peak was detected in EDX analysis for
pristine and doped ZnO samples. The above results reveals that the ZnO
D = (K λ)/(β cos θ) (1) product is highly pure having no surfactant or by-product and Ag and

222
A. Saboor et al. Materials Science in Semiconductor Processing 93 (2019) 215–225

Nd impurities have been successfully incorporated into the lattice of structure seems to make the incorporation of Ag1 + impurity highly
ZnO. fruitful to raise the stability of surface. Thus, this process may con-
siderably reduce Zn2 + dye aggregates, and therefore sufficient mole-
3.4. Optical study of the nanohybrid materials cules of dye are chemisorbed over the electrode surface. Compared to
pristine ZnO and Ag-doped ZnO electrode, Nd-doped ZnO electrodes
For the synthesis of nanohybrid assembly, Bromopyrogallol Red Dye show decreased circuit current density. This decrease could also be
(Br-PGR) was grafted over the surface of pristine ZnO, Ag-ZnO and Nd- associated to the presence of un-doped Nd and the formation of Nd2O3
ZnO nanorods (more detail is given in the experimental section). as an additional phase [78]. The enhancement or decrease in the
photovoltaic performance is mechanistically explained with the help of
3.4.1. Optical study of nanohybrid material energy level diagram shown below in Fig. 10.
The UV–visible absorption spectra of Bromopyrogallol red dye and The energy level diagram was constructed from the calculated band
the nanohybrid material (pristine/doped ZnO-Br-PGR) are shown in gap of Ag and Nd-doped ZnO nanorods. The calculated conduction band
Fig. 8. The Br-PGR shows two absorption bands, one broad absorption minimum (CBM) value is schematically shown in Fig. 10. From this
band at 555 nm in the visible region ascribed to n→π* transition while diagram, it can be noticed that the improvement in the efficiency of Ag-
the other is a small absorption peak centered at 346.5 nm in the UV doped ZnO dye sensitized solar cell could be assigned to a little shift in
region assigned to π → π* transition due to aromatic moieties. the CBM towards the lower energy state. This tends to shift the con-
Br-PGR was grafted onto the surface of pristine ZnO, Ag-doped ZnO duction band minimum (CBM) slightly away from the LUMO level of
and Nd-doped ZnO nanorods in the same concentration (7 mM) using Br-PGR and makes an effortless transfer of photo exited electrons to-
methanol as a solvent. When the dye (Br-PGR) was chemisorbed on the wards the conduction band of photo-anode as compared to pure ZnO
surface of pristine/doped ZnO nanorods, exciting changes were ob- photoanode. Nevertheless, in case of Nd-doped ZnO photoanode, CBM
served in optical behavior. The UV–visible spectrum of dye in the moves far away from the LUMO level of dye but more closer to HOMO
visible region was overlaid by the absorption spectra of grafted samples level of the dye. In case of Nd-doped ZnO, the CBM of doped sample is
(pristine/doped ZnO-Br-PGR) as shown in Fig. 8. Optical absorption much closer to HOMO level of Br-PGR, as a result the photo-induced
spectra of grafted samples become much broader and red-shifted with hole in HOMO will combine with the electron present in conduction
absorption maxima at 616.5 nm, 611 nm and 606 nm respectively. This band of Nd-doped ZnO which leads to a decline in current density and
significant rise in the intensity of absorption band and bathochromic affects the overall efficiency of the cell [79].
shift reveals that the dye is successfully chemisorbed over the surface of All the characteristic parameters of solar cell obtained from the
nanorods [74–76]. Furthermore this remarkable increase in absorption above I-V plots are listed in Table 3.
coefficient of the nanohybrid samples and the bathochromic shift could
boost the efficiency of hybrid solar cells in comparison to bare nanorods 4. Conclusion
and dye alone [77].
Pristine ZnO, Ag-doped ZnO, and Nd-doped ZnO nanorods were
3.4.2. Photovoltaic performance successfully prepared by hydrothermal method. Detailed analysis of
Hybrid heterojunction solar cells were designed using the nano- optical, electrical, structural and photovoltaic properties of pristine and
hybrid assembly; pristine/doped ZnO nanorods sensitized with Br-PGR doped ZnO nanorods declared that Ag and Nd content in the nanorods
as photoactive blend. The photoactive blend was mixed with an organic have conspicuous effect on the properties of ZnO. A remarkable de-
semiconducting polymer, (P3HT). I-V measurements of these cells were crease in the band gap of ZnO nanorods was noticed with varying Ag
plotted to study photovoltaic performance with regards to several im- and Nd doping concentration. The band gap (Tauc plot) of ZnO na-
portant parameters such as open circuit voltage (Voc), short circuit norods was reduced to 2.64 and 2.65 eV for 3% Ag-doped ZnO and 7%
current (Jsc), fill factor (FF), maximum power point (Mpp) and the Nd-doped ZnO respectively. XRD pattern showed that the nanorods are
overall percent efficiency (η %). highly crystalline and no extra phase is indicated but in case of the Ag-
I-V measurements were performed for fabricated DSSCs which are doped ZnO nanorods samples, some additional peaks are formed which
based on the pristine ZnO, Ag-doped ZnO and Nd-doped ZnO grafted are associated with the face-centered-cubic phase of metallic Ag. SEM
with the same concentration of dye and blended with P3HT. This is images confirm the formation of nanorods having smooth surface with
shown in Fig. 9. The solar cell based on bare ZnO nanorods blended an average crystalline size of 131 nm for pristine ZnO, 207 nm for Ag-
with P3HT was used as reference device which gave no current in the doped ZnO and 222 nm for Nd-doped ZnO nanorods. There is a large
dark. When these fabricated DSSC's were subjected to a light source of bathochromic shift when dye is chemisorbed over the surface of pristine
100 mW/cm2 using solar simulator, some amount of current was re- and doped ZnO nanorods which indicates that bromopyrogallol red dye
gistered. A notable rise in value of short circuit current (Jsc) was ob- can be used successfully for the light harvesting in dye sensitized solar
served for doped ZnO nanorods grafted with bromopyrogallol red dye. cells. The hybrid solar cell was characterized by Current-Voltage mea-
The Ag-doped ZnO nanorods grafted with bromopyrogallol red dye surements. The conversion efficiency of the doped ZnO nanorods was
showed maximum current density. found better than pristine ZnO nanorods and maximum efficiency of 1%
Table 3 lists the numerical values of the open circuit voltages (Voc), was noticed for Ag-doped ZnO nanorods.
short circuit current (Jsc), fill factors and efficiencies (η %) of all the
devices along with the reference device. The DSSC employing 7 mol% Acknowledgement
of Ag-doped ZnO photoanode showed nice performance with an effi-
ciency (η) of 1% which is the best among all our fabricated DSSCs under We are highly thankful to the Higher Education Commission of
the same experimental conditions. This increment in current density Pakistan under project No. 6169/Federal//NRPU/R&D/HEC/16 for fi-
might be partially ascribed to increase in conductivity of semiconductor nancial support and Quaid-i-Azam University, Islamabad, for providing
by the incorporation of doping agent (Ag) in the crystal lattice of ZnO laboratory and space facilities.
nanorods influencing either the surface chemistry or morphology of the
ZnO nanorods plus the photoelectrode film and partially to the band References
gap tuning(decreasing band gap) of the material to the visible region.
This indicates that the surface network of Ag-doped ZnO is significantly [1] J.-S. Huang, T. Goh, X. Li, M.Y. Sfeir, E.A. Bielinski, S. Tomasulo, M.L. Lee,
reinforced than that of pristine ZnO photoanode. The preferential re- N. Hazari, A.D. Taylor, Polymer bulk heterojunction solar cells employing Förster
resonance energy transfer, Nat. Photonics 7 (2013) 479.
placement of Zn2 + ions by Ag1+ ions inside the wurtzite crystal

223
A. Saboor et al. Materials Science in Semiconductor Processing 93 (2019) 215–225

[2] J. Peet, J.Y. Kim, N.E. Coates, W.L. Ma, D. Moses, A.J. Heeger, G.C. Bazan, 9–16.
Efficiency enhancement in low-bandgap polymer solar cells by processing with [31] M. Law, L.E. Greene, J.C. Johnson, R. Saykally, P. Yang, Nanowire dye-sensitized
alkane dithiols, Nat. Mater. 6 (2007) 497. solar cells, Nat. Mater. 4 (6) (2005) 455.
[3] J.A. Anta, E. Guillen, R. Tena-Zaera, ZnO-based dye-sensitized solar cells, J. Phys. [32] H. Tributsch, H. Gerischer, The use of semiconductor electrodes in the study of
Chem. C. 116 (21) (2012) 11413–11425. photochemical reactions, Ber. der Bunsenges. für Phys. Chem. 73 (8‐9) (1969)
[4] A. Hagfeldt, G. Boschloo, L. Sun, L. Kloo, H. Pettersson, Dye-sensitized solar cells, 850–854.
Chem. Rev. 110 (2010) 6595–6663. [33] Q. Zhang, C.S. Dandeneau, X. Zhou, G. Cao, ZnO nanostructures for dye‐sensitized
[5] S.K. Balasingam, M.G. Kang, Y. Jun, Metal substrate based electrodes for flexible solar cells, Adv. Mater. 21 (41) (2009) 4087–4108.
dye-sensitized solar cells: fabrication methods, progress and challenges, Chem. [34] D.C. Olson, J. Piris, R.T. Collins, S.E. Shaheen, D.S. Ginley, Hybrid photovoltaic
Commun. 49 (2013) 11457–11475. devices of polymer and ZnO nanofiber composites, Thin Solid films 496 (2006)
[6] S. Mathew, A. Yella, P. Gao, R. Humphry-Baker, B.F.E. Curchod, N. Ashari-Astani, 26–29.
I. Tavernelli, U. Rothlisberger, M.K. Nazeeruddin, M. Grätzel, Dye-sensitized solar [35] B. Conings, L. Baeten, H.-G. Boyen, J. D’Haen, M.K. Van Bael, J.V. Manca, Relation
cells with 13% efficiency achieved through the molecular engineering of porphyrin between morphology and recombination kinetics in nanostructured hybrid solar
sensitizers, Nat. Chem. 6 (2014) 242. cells, J. Phys. Chem. C 116 (2012) 14237–14242.
[7] A. Yella, H.-W. Lee, H.N. Tsao, C. Yi, A.K. Chandiran, M.K. Nazeeruddin, E.W.- [36] S. Shoaee, J. Briscoe, J.R. Durrant, S. Dunn, Acoustic enhancement of polymer/ZnO
G. Diau, C.-Y. Yeh, S.M. Zakeeruddin, M. Grätzel, Porphyrin-sensitized solar cells nanorod photovoltaic device performance, Adv. Mater. 26 (2014) 263–268.
with cobalt(II/III)–based redox electrolyte exceed 12 percent efficiency, science 334 [37] J. Han, Z. Liu, X. Zheng, K. Guo, X. Zhang, T. Hong, B. Wang, J. Liu, Trilaminar
(2011) 629–634. ZnO/ZnS/Sb2S3 nanotube arrays for efficient inorganic–organic hybrid solar cells,
[8] A. Hagfeldt, G. Boschloo, L. Sun, L. Kloo, H. Pettersson, Dye-sensitized solar cells, Rsc Adv. 4 (2014) 23807–23814.
Chem. Rev. 110 (2010) 6595–6663. [38] Y.-Z. Zheng, H. Ding, Y. Liu, X. Tao, G. Cao, J.-F. Chen, In-situ hydrothermal growth
[9] D.P. Hagberg, T. Marinado, K.M. Karlsson, K. Nonomura, P. Qin, G. Boschloo, of bi-hierarchical ZnO nanoarchitecture with surface modification for efficient hy-
T. Brinck, A. Hagfeldt, L. Sun, Tuning the HOMO and LUMO energy levels of or- brid solar cells, Electrochim. Acta 145 (2014) 116–122.
ganic chromophores for dye sensitized solar cells, J. Org. Chem. 72 (2007) [39] L. Whittaker‐Brooks, W.E. McClain, J. Schwartz, Y.L. Loo, Donor‐acceptor inter-
9550–9556. facial interactions dominate device performance in hybrid P3HT‐ZnO
[10] M. Grätzel, Recent advances in sensitized mesoscopic solar cells, Acc. Chem. Res. 42 Nanowire‐array solar cells, Adv. Energy Mater. 4 (2014) 1400585.
(2009) 1788–1798. [40] R.T. Ginting, C.C. Yap, M. Yahaya, M.M. Salleh, Improvement of inverted type
[11] A. Mishra, M.K. Fischer, P. Bäuerle, Metal‐free organic dyes for dye‐sensitized solar organic solar cells performance by incorporating Mg dopant into hydrothermally
cells: from structure: property relationships to design rules, Angew. Chem. Int. Ed. grown ZnO nanorod arrays, J. Alloy. Compd. 585 (2014) 696–702.
48 (2009) 2474–2499. [41] R.T. Ginting, C.C. Yap, M. Yahaya, M. Mat Salleh, Solution-processed Ga-doped ZnO
[12] M. Pastore, S. Fantacci, F. De Angelis, Ab initio determination of ground and excited nanorod arrays as electron acceptors in organic solar cells, ACS Appl. Mater.
state oxidation potentials of organic chromophores for dye-sensitized solar cells, J. Interfaces 6 (2014) 5308–5318.
Phys. Chem. C 114 (2010) 22742–22750. [42] P. Ruankham, T. Sagawa, H. Sakaguchi, S. Yoshikawa, Vertically aligned ZnO na-
[13] J. Liu, R. Li, X. Si, D. Zhou, Y. Shi, Y. Wang, X. Jing, P. Wang, Oligothiophene dye- norods doped with lithium for polymer solar cells: defect related photovoltaic
sensitized solar cells, Energy Environ. Sci. 3 (2010) 1924–1928. properties, J. Mater. Chem. 21 (2011) 9710–9715.
[14] J. Liu, D. Zhou, M. Xu, X. Jing, P. Wang, The structure–property relationship of [43] Y. Ryu, S. Zhu, D.C. Look, J. Wrobel, H. Jeong, H. White, Synthesis of p-type ZnO
organic dyes in mesoscopic titania solar cells: only one double-bond difference, films, J. Cryst. Growth 216 (2000) 330–334.
Energy Environ. Sci. 4 (2011) 3545–3551. [44] B. Xiang, P. Wang, X. Zhang, S.A. Dayeh, D.P. Aplin, C. Soci, D. Yu, D. Wang,
[15] M.K. Nazeeruddin, E. Baranoff, M. Grätzel, Dye-sensitized solar cells: a brief over- Rational synthesis of p-type zinc oxide nanowire arrays using simple chemical
view, Sol. Energy 85 (2011) 1172–1178. vapor deposition, Nano Lett. 7 (2007) 323–328.
[16] S. Ito, S.M. Zakeeruddin, R. Humphry‐Baker, P. Liska, R. Charvet, P. Comte, [45] R. Zamiri, A. Lemos, A. Reblo, H.A. Ahangar, J. Ferreira, Effects of rare-earth (Er, La
M.K. Nazeeruddin, P. Péchy, M. Takata, H. Miura, High‐efficiency organic‐dye‐- and Yb) doping on morphology and structure properties of ZnO nanostructures
sensitized solar cells controlled by nanocrystalline‐TiO2 electrode thickness, Adv. prepared by wet chemical method, Ceram. Int. 40 (2014) 523–529.
Mater. 18 (2006) 1202–1205. [46] O. Lupan, L. Chow, L.K. Ono, B.R. Cuenya, G. Chai, H. Khallaf, S. Park, A. Schulte,
[17] M.K. Nazeeruddin, P. Pechy, T. Renouard, S.M. Zakeeruddin, R. Humphry-Baker, Synthesis and characterization of Ag-or Sb-doped ZnO nanorods by a facile hy-
P. Comte, P. Liska, L. Cevey, E. Costa, V. Shklover, Engineering of efficient pan- drothermal route, J. Phys. Chem. C 114 (2010) 12401–12408.
chromatic sensitizers for nanocrystalline TiO2-based solar cells, J. Am. Chem. Soc. [47] T. Pauporte, O. Lupan, J. Zhang, T. Tugsuz, I. Ciofini, Fdr Labat, B. Viana, Low-
123 (2001) 1613–1624. temperature preparation of Ag-doped ZnO nanowire arrays, DFT study, and appli-
[18] A. Yella, H.-W. Lee, H.N. Tsao, C. Yi, A.K. Chandiran, M.K. Nazeeruddin, E.W.- cation to light-emitting diode, ACS Appl. Mater. Interfaces 7 (2015) 11871–11880.
G. Diau, C.-Y. Yeh, S.M. Zakeeruddin, M. Grätzel, Porphyrin-sensitized solar cells [48] Y. Liu, W. Luo, R. Li, X. Chen, Optical properties of Nd3+ ion-doped ZnO nano-
with cobalt(II/III)–based redox electrolyte exceed 12 percent efficiency, science 334 crystals, J. Nanosci. Nanotechnol. 10 (2010) 1871–1876.
(2011) 629–634. [49] F. Xian, X. Li, Effect of Nd doping level on optical and structural properties of
[19] S.M. Feldt, E.A. Gibson, E. Gabrielsson, L. Sun, G. Boschloo, A. Hagfeldt, Design of ZnO:Nd thin films synthesized by the sol–gel route, Opt. Laser Technol. 45 (2013)
organic dyes and cobalt polypyridine redox mediators for high-efficiency dye-sen- 508–512.
sitized solar cells, J. Am. Chem. Soc. 132 (2010) 16714–16724. [50] D.C. Olson, S.E. Shaheen, M.S. White, W.J. Mitchell, M.F. van Hest, R.T. Collins,
[20] U. Bach, D. Lupo, P. Comte, J. Moser, F. Weissörtel, J. Salbeck, H. Spreitzer, D.S. Ginley, Band‐offset engineering for enhanced open‐circuit voltage in poly-
M. Grätzel, Solid-state dye-sensitized mesoporous TiO2 solar cells with high photon- mer–oxide hybrid solar cells, Adv. Funct. Mater. 17 (2007) 264–269.
to-electron conversion efficiencies, Nature 395 (1998) 583. [51] F.C. Romeiro, J.Z. Marinho, A.C.A. Silva, N.F. Cano, N.O. Dantas, R.C. Lima,
[21] J. Burschka, A. Dualeh, F. Kessler, E. Baranoff, N.-L. Cevey-Ha, C. Yi, Photoluminescence and magnetism in Mn2+-doped ZnO nanostructures grown ra-
M.K. Nazeeruddin, M. Grätzel, Tris (2-(1H-pyrazol-1-yl) pyridine) cobalt(III) as p- pidly by the microwave hydrothermal method, J. Phys. Chem. C 117 (2013)
type dopant for organic semiconductors and its application in highly efficient solid- 26222–26227.
state dye-sensitized solar cells, J. Am. Chem. Soc. 133 (2011) 18042–18045. [52] T.-H. Lee, H.-J. Sue, X. Cheng, Solid-state dye-sensitized solar cells based on ZnO
[22] D. Gebeyehu, C. Brabec, N. Sariciftci, D. Vangeneugden, R. Kiebooms, nanoparticle and nanorod array hybrid photoanodes, Nanoscale Res. Lett. 6 (2011)
D. Vanderzande, F. Kienberger, H. Schindler, Hybrid solar cells based on dye-sen- 517.
sitized nanoporous TiO2 electrodes and conjugated polymers as hole transport [53] N. Shahzad, S.M. Shah, S. Munir, A. Hana, U. Jabeen, E. Nosheen, B. Habib,
materials, Synth. Met. 125 (2001) 279–287. A.U. Khan, Z. Hassan, M. Siddiq, Charge-transfer complexation at carminic
[23] K. Sayama, H. Sugihara, H. Arakawa, Photoelectrochemical properties of a porous acid–CdS interface and its impact on the efficiency of dye-sensitized solar cells, J.
Nb2O5 electrode sensitized by a ruthenium dye, Chem. Mater. 10 (1998) Electron. Mater. 44 (2015) 1167–1174.
3825–3832. [54] R. Wahab, S. Ansari, Y. Kim, H. Seo, G. Kim, G. Khang, H.-S. Shin, Low temperature
[24] Y. Fukai, Y. Kondo, S. Mori, E. Suzuki, Highly efficient dye-sensitized SnO2 solar solution synthesis and characterization of ZnO nano-flowers, Mater. Res. Bull. 42
cells having sufficient electron diffusion length, Electrochem. Commun. 9 (2007) (2007) 1640–1648.
1439–1443. [55] Y. Zhang, Z. Zhang, B. Lin, Z. Fu, J. Xu, Effects of Ag doping on the photo-
[25] Z. Wang, X.-f. Qian, J. Yin, Z.-k. Zhu, Large-scale fabrication of tower-like, flower- luminescence of ZnO films grown on Si substrates, J. Phys. Chem. B 109 (41) (2005)
like, and tube-like ZnO arrays by a simple chemical solution route, Langmuir 20 19200–19203.
(2004) 3441–3448. [56] J. Fan, R. Freer, The roles played by Ag and Al dopants in controlling the electrical
[26] Q. Zhang, C.S. Dandeneau, S. Candelaria, D. Liu, B.B. Garcia, X. Zhou, Y.-H. Jeong, properties of ZnO varistors, J. Appl. Phys. 77 (9) (1995) 4795–4800.
G. Cao, Effects of lithium ions on dye-sensitized ZnO aggregate solar cells, Chem. [57] C.E. Kim, P. Moon, S. Kim, J.-M. Myoung, H.W. Jang, J. Bang, I. Yun, Effect of
Mater. 22 (2010) 2427–2433. carrier concentration on optical bandgap shift in ZnO:Ga thin films, Thin Solid
[27] Z.L. Wang, J. Song, Piezoelectric nanogenerators based on zinc oxide nanowire Films 518 (2010) 6304–6307.
arrays, Science 312 (2006) 242–246. [58] B.K. Kaleji, R. Sarraf-Mamoory, A. Fujishima, Influence of Nb dopant on the
[28] Z. Fan, D. Wang, P.-C. Chang, W.-Y. Tseng, J.G. Lu, ZnO nanowire field-effect structural and optical properties of nanocrystalline TiO2 thin films, Mater. Chem.
transistor and oxygen sensing property, Appl. Phys. Lett. 85 (2004) 5923–5925. Phys. 132 (2012) 210–215.
[29] R. Borgohain, S. Baruah, Design and analysis of UV detector using ZnO nanorods on [59] V. Štengl, S. Bakardjieva, N. Murafa, Preparation and photocatalytic activity of rare
interdigitated electrodes, ADBU J. Eng. Technol. (2016) 4. earth doped TiO2 nanoparticles, Mater. Chem. Phys. 114 (2009) 217–226.
[30] A. Yu, J. Qian, H. Pan, Y. Cui, M. Xu, L. Tu, Q. Chai, X. Zhou, Micro-lotus con- [60] Y. Zhou, S. Lu, W. Xu, Photocatalytic activity of Nd‐doped ZnO for the degradation
structed by Fe-doped ZnO hierarchically porous nanosheets: preparation, char- of CI reactive blue 4 in aqueous suspension, Environ. Progress. Sustain. Energy.: Off.
acterization and gas sensing property, Sens. Actuators B: Chem. 158 (1) (2011) Publ. Am. Inst. Chem. Eng. 28 (2009) 226–233.

224
A. Saboor et al. Materials Science in Semiconductor Processing 93 (2019) 215–225

[61] Y. Liu, W. Luo, R. Li, X. Chen, Optical properties of Nd3+ ion-doped ZnO nano- of neodymium doped zinc oxide thin films, Mater. Lett. 65 (2011) 2345–2347.
crystals, J. Nanosci. Nanotechnol. 10 (2010) 1871–1876. [72] K. Mahmood, B.S. Swain, G.S. Han, B.J. Kim, H.S. Jung, Polyethylenimine-assisted
[62] C. Persson, C. Platzer-Björkman, J. Malmström, T. Törndahl, M. Edoff, Strong va- growth of high-aspect-ratio nitrogen-doped ZnO (NZO) nanorod arrays and their
lence-band offset bowing of ZnO1−xSx enhances p-type nitrogen doping of ZnO-like effect on performance of dye-sensitized solar cells, ACS Appl. Mater. Interfaces 6
alloys, Phys. Rev. Lett. 97 (14) (2006) 146403. (13) (2014) 10028–10043.
[63] American Society for Testing and Material. Powder Diffraction Files; Joint [73] M.A. Thomas, W.W. Sun, J.B. Cui, Mechanism of Ag doping in ZnO nanowires by
Committee on Powder Diffraction Standards: Swarthmore, PA, pp 3–888. electrodeposition: experimental and theoretical insights, J. Phys. Chem. C 116 (10)
[64] R. Georgekutty, M.K. Seery, S.C. Pillai, A highly efficient Ag-ZnO photocatalyst: (2012) 6383–6391.
synthesis, properties, and mechanism, J. Phys. Chem. C 112 (2008) 13563–13570. [74] L. Martín-Gomisa, E.M. Barea, F. Fernández-Lázaroa, J. Bisquert, Á. Sastre-Santos,
[65] C. Chen, Y. Zheng, Y. Zhan, X. Lin, Q. Zheng, K. Wei, Enhanced Raman scattering Dye sensitized solar cells using non-aggregated silicon phthalocyanines, J. Porphyr.
and photocatalytic activity of Ag/ZnO heterojunction nanocrystals, Dalton Trans. Phthalocyanines 15 (2011) 1004–1010.
40 (2011) 9566–9570. [75] P. Maity, T. Debnath, U. Chopra, H.N. Ghosh, Cascading electron and hole transfer
[66] H.S. Kang, B.D. Ahn, J.H. Kim, G.H. Kim, S.H. Lim, H.W. Chang, S.Y. Lee, Structural, dynamics in a CdS/CdTe core–shell sensitized with bromo-pyrogallol red (Br-PGR):
electrical, and optical properties of p-type ZnO thin films with Ag dopant, Appl. slow charge recombination in type II regime, Nanoscale 7 (2015) 2698–2707.
Phys. Lett. 88 (20) (2006) 202108. [76] T. Debnath, P. Maity, S. Maiti, H.N. Ghosh, Electron trap to electron storage center
[67] H. Xue, X.L. Xu, Y. Chen, G.H. Zhang, S.Y. Ma, Influence of Ag-doping on the optical in specially aligned Mn-doped CdSe d-Dot: a step forward in the design of higher
properties of ZnO films, Appl. Surf. Sci. 255 (5) (2008) 1806–1810. efficient quantum-dot solar cell, J. Phys. Chem. Lett. 5 (2014) 2836–2842.
[68] Z.Y. Lv, Y. Zhao, Z. Li, X.Y. Liang, Z.J. Hou, L.J. Wang, J.H. Min, Photoluminescence [77] Y. Gao, X. Zou, Z. Sun, Z. Huang, H. Zhou, Enhancement of electron transfer effi-
and Raman scattering of Cu-N codoped ZnO thin films, App. Mech. Mater. (2012) ciency in solar cells based on PbS QD/N719 dye cosensitizers, J. Nanomater. 2012
565–570 (Trans Tech Publications). (2012) 8.
[69] M.M. Khan, S.A. Ansari, M.I. Amal, J. Lee, M.H. Cho, Highly visible light active [78] B. Roy, S. Chakrabarty, O. Mondal, M. Pal, A. Dutta, Effect of neodymium doping on
Ag@TiO2 nanocomposites synthesized using an electrochemically active biofilm: a structure, electrical and optical properties of nanocrystalline ZnO, Mater. Charact.
novel biogenic approach, Nanoscale 5 (2013) 4427–4435. 70 (2012) 1–7.
[70] P.K. Nayak, J. Yang, J. Kim, S. Chung, J. Jeong, C. Lee, Y. Hong, Spin-coated Ga- [79] C.J. Raj, K. Prabakar, S.N. Karthick, K.V. Hemalatha, M.K. Son, H.J. Kim, Banyan
doped ZnO transparent conducting thin films for organic light-emitting diodes, J. root structured Mg-doped ZnO photoanode dye-sensitized solar cells, J. Phys. Chem.
Phys. D: Appl. Phys. 42 (2008) 035102. C 117 (6) (2013) 2600–2607.
[71] Z. Huang, P. Luo, M. Chen, S. Pan, D. Chen, Microstructure and hemocompatibility

225