Article
Effect of ZnO Nanoparticles Coating Layers on Top
of ZnO Nanowires for Morphological, Optical, and
Photovoltaic Properties of Dye-Sensitized Solar Cells
Muhammad Saleem 1, W. A. Farooq 2,*, M. I. Khan 3, Majid. Niaz. Akhtar 4, Saif Ur Rehman 5,
Naseeb Ahmad 1, Muhammad Khalid 6, M. Atif 2, Mona A. AlMutairi 2 and Muhammad Irfan 7
1 Department of Physics, Khwaja Freed University of Engineering and Information Technology, Rahim Yar
Khan 64200, Pakistan;
[email protected] (M.S.);
[email protected] (N.A.)
2 Department of Physics and Astronomy, College of Science, King Saud University, Riyadh 11451, Saudi
3 Department of Physics, The University of Lahore, Lahore 53700, Pakistan;
[email protected] 4 Department of Physics, Muhammad Nawaz Sharif (MNS) University of Engineering and Technology,
5 Department of Physics, COMSATS University Islamabad, Lahore 54000, Pakistan;
[email protected] 6 Department of Chemistry, Khwaja Fareed University of Engineering and Information Technology, Rahim
7 CAS Key Laboratory of strongly Coupled Quantum matter Physics, USTC, Hefei 230026, China;
[email protected]
* Correspondence: [email protected]
Received: 25 August 2019; Accepted: 20 November 2019; Published: 26 November 2019
Abstract: This paper reports on the synthesis of ZnO nanowires (NWs), as well asthe compound
nanostructures of nanoparticles (NPs) and nanowires (NWs+NPs) with different coating layers of
NPs on the top of NWs and their integration in dye-sensitized solar cells (DSSCs). In compound
nanostructures, NWs offer direct electrical pathways for fast electron transfer, and the NPs of
ZnOdispread and fill the interstices between the NWs of ZnO, offering a huge surface area for
enough dye anchoring and promoting light harvesting. A significant photocurrent density of 2.64
mA/cm2 and energy conversion efficiency of 1.43% was obtained with NWs-based DSSCs. The total
solar-to-electric energy conversion efficiency of the NWs+a single layer of NPs was found to be
2.28%, with a short-circuit photocurrent density (JSC) of 3.02 mA/cm2, open-circuit voltage (VOC) of
0.74 V, and a fill factor (FF) of 0.76, which is 60% higher than that of NWs cells and over 165% higher
than NWs+a triple layer of NPs-based DSSCs. The improved performance was obtained due to the
increased specific surface area for higher dye anchoring and light harvesting of compound
nanostructures with NWs+a single layer of NPs.
Keywords:DSSCs; coating layers of NPs; nanowires
1. Introduction
Dye-sensitized solar cells (DSSCs) are considered promising devices for energy harvesting and
large-scale fabrication due to their relatively high efficiency, costeffectiveness, and simple
preparation process [1,2]. Many types of photovoltaic devices have been inducted in the market
during the last 50 years [3–5]. However, their large-scale utility is still limited due to some challenges
related to their stability, durability, the number of interparticle hops, and the low surface area [6–8].
So for, many ZnO photoanode architectures such as nanowires [9–11], nanobelts [12,13],
nanoparticles [14–16], and nanotubes [10,17,18] have been fabricated for DSSCs. Recently, one-
dimensional (1D) ZnO nanostructures have been extensively studied, which have the capacity to
Micromachines 2019, 10, 819; doi:10.3390/mi10120819 www.mdpi.com/journal/micromachines
Micromachines 2019, 10, 819 2 of 11
provide a direct pathway and less trapping sites than the random network for the fast collection of
photogenerated electrons, and thereby reduce the number of interparticle hops [19–23]. However,
such 1D nanostructures seem to have insufficient surface area, which constrains solar-to-electric
energy conversion efficiency to a relatively low level compared to TiO2 nanostructures. Therefore,
one way to further boost the efficiency of a cell is to pull off the light-harvesting ability of the
photoelectrode film. One effective way to overcome these problems is either by utilizing optical
enhancement effects, which can be achieved by mixing NPs with ZnO NWs, or by using a
nanospheres film instead of a nanoparticles film. In several studies, different fractions (mass ratio) of
NPs of ZnO/TiO2 were mixed with ZnO/TiO2 nanowires, nanorods, and nanofibers for affording a
rapid electron conduction pathway and enlarging a dye adsorption area for increasing cell
performance [24–29]. However, for significant enhancement in the overall performance of the cell,
we still need an increase in the surface area of nanowire arrays [30].
Herein, we have made the use of ZnO nanowires (NWs) and compound nanostructures of ZnO
nanowires and nanoparticles (NWs + NPs) with different coating layers of NPs on top of NWs as the
photoelectrodes in DSSCs. The key point of this study is the coating of single, double, and triple layers
of NPs and to study the effect of the coating layers’ thickness on the morphological, optical and
photovoltaic properties of DSSCs. To enhance the performance of ZnO NWs DSSCs, nanoparticles of
ZnO were filled in the interstices of NWs to achieve a fast electron transport pathway and to enlarge
the dye adsorption area. Surprisingly, it is noted that DSSCs fabricated with double and triple layer
coatingsof NPs show worse performance than those of NWs/NWs with a single layer of NPs. This
can be due to the increased thickness, as an overly thick film aggravates unnecessary charge
recombination and poses more constraint on mass transfer. Thus, we can infer that the appropriate
content of NP incorporation into the NWs can promote the dye adsorption, transport the electrons,
decrease the charge recombination, and thereby increase the performance of the cells.
2. Experimental
2.1. Synthesis of ZnO Nanoparticles
NPs of ZnO were synthesized by dissolving 2.96 g of zinc acetate dihydrate (Zn
(CH3COO)2.2H2O, Merck, Kenilworth, NJ, USA) (ZAD) in 150 mL of diethylene glycol (C4H10O3,
Merck, Kenilworth, NJ, USA) (DEG) in a conical flask. The synthesis was performed in the following
steps:(i) prepare the solution, (ii) heat it for hydrolysis, and (iii) heat treatment of the final samples.
The experimental flask was fitted with a thermometer (Figure 1) and placed on hot stirrer, under
continuous stirring. The heating of solution was carried out to 500 °C at a rate of 6 °C/min. When the
temperature of the clear solution reached 180°C, the solution first turned yellow and then into a milky
white color. The temperature of the solution was fixed at 180°C for 15 min and then stopped heating.
When the reaction stopped and the temperature of the solution reached 26 °C, the white precipitate
was collected by centrifuge and washed three times with ethanol. The powder was placed in a furnace
at 400°C for 1h to remove extra residual organics.
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Figure 1. Procedure of the experiment.
2.2. ZnO Nanowire Arraysand Nanoparticle Compound Structures Synthesis
ZnO NWs arrays were synthesized in an aqueous solution, using a two-step process described
elsewhere [31]. NWs were grown by immersing the seeded FTO substrates vertically in glass bottles
containing 55 mL of solution. The growth solution consists of 1.09 g of zinc nitrate hexahydrate
(ZNH), 0.70 g hexamethylenetetramine (HMTA), and 0.4 M ammonium hydroxide (NH4OH). Then,
the bottles were covered and placed in an electric oven at 95 °C for 4 h. After growth, the substrates
were immediately washed with distilled water. Finally, the NWs grown on substrates were backed
at 450 °C for 30 min to remove excess solvent. The samples were prepared using spincoating. The
concentration of ZnO nanoparticles synthesized in DEG at 500 °C at a rate of 6 °C/min) was 0.2 g in
30 mL of acetone. One sample consist only nanowires (NWs), the second sample was composed of
nanowires and a single layer of nanoparticles (NWs+single layer of NPs), the third sample was
composed of NWs and a double layer of NPs(NWs+double layer of NPs), and the fourth sample was
composed of NWs and three layers of NPs (NWs+triple layer of NPs), as shown in Figure 2.The speed
of the spin coater for the grown ZnO NPs onto NWs was 2500 rpm for 30 s. After each spincoating,
the films were placed into a furnace for heating at 200 °C for 10 min to evaporate the solvent. This
procedure of spinning to preheating was repeated three times for the sample having a triple layer of
NWs+NPs.
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Figure 2. SEM images of the ZnO nanoproducts.
2.3. Measurements and Characterizations
XRD patterns were measured by X-ray diffraction (XRD, Bruker D2 Phaser, Beerlika, MA, USA)
using a 2θ scan. A scanning electron microscope study was done by SEM (model: JEOL JSM-7600F,
Tokyo, Japan). I–V measurements of DSSCs were taken out with a Keithley 2400 source meter under
an AM 1.5 global air mass filter, and the voltage sweep rate was 0.01V/s. The optical properties after
dye loading were examined using a Perkenelmer Lambda-750 UV-VIS NIR spectrophotometer.
2.4. Cell Assembly
The effective area of photoelectrodes was 0.5 cm × 0.5 cm = 0.25 cm2. Dyeing was carried out by
dipping these films in solutions of N719 dye for 3 h, and the films were then removed from the dye
solution. The dyed films were rinsed off with acetonitrile to remove an excess of N719 dye remaining
on the surface of the films. The dye was prepared by 0.5 mMof di-tertbutylpyridylcis–bis“(4,4'-
dicarboxy-2,2'-bipyridine)dithiocyanato ruthenium(II)”, in a 1:1 mixture of acetonitrile. After dyeing,
DSSCs were assembled by placing Pt-coated (8 Ω·cm−1) counter electrodes on prepared
photoelectrodes separated by 30 µm of hot-melt surlyn film. The iodide/tri-iodide electrolyte
consisting of 0.05 M I2 and 0.5 M 1,2-dimethyl-3-propylimidazolium iodide in acetonitrile was filed
between the space of each cell by capillary action. Finally, three cells of each sample were fabricated
and tested to check the reproducibility and almost similar results of I–V measurement happened.
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3. Results and Discussion
3.1. Structural Analysis
Figure 3 depicts the crystalline orientation of the ZnO NWs, NWs+a single layer of NPs, NWs+a
double layer of NPs, and NWs+a triple layer of NPs compound structures determined by XRD. The
XRD peaks of all the structures correspond to2𝜃 = 31.7° 100 , 34.4° 002 , 36.5° 101 , 47.7° 102 ,
56.8° 110 , 63.1° 103 , 66.5° 200 , 68.1° 112 , 69.2° 201 planes of ZnO. The XRD data also
show the wurtzite structure of ZnO. These planes agreed well with the standard reported values
(JCPDS file No. 36-1451). There are no diffraction peaks corresponding to impurities such as Zn and
Zn (OH)2.The crystallite size of nanoparticles was calculated for the (101) peak due to high intensity
using the Scherrer equation [31]. The calculated size of nanocrystallites was 20 nm. The intensity of
peaks increases with the increase in thickness due to the growth of NP layers. All the peaks are
slightly shifted toward right with the addition of NPs and the absence of any other peak confirms the
high purity of the hexagonal ZnO phase and the good alignment of the samples. It is noteworthy that
the intensity of (101) is strongest among the other reflections.
Figure 3. X-ray diffraction(XRD) patterns of the ZnO nanoproducts.
3.2. Morphological Analysis
The crystallographic morphologies of the NWs of ZnO, NWs+a single layer of NPs, NWs+a
double layer of NPs, and NWs+a triple layer of NPs were observed using FESEM. From Figure 2, it
can be seen that the alignment is good, and the NWs are vertically grown on the substrates (FTO)
with a length of about 1.1 µm. As a result, such a type of one-dimensional nanostructured-based
photoelectrode film has insufficient surface area. If the interstitial voids between the NWs might be
filled with NPs, the photoelectrodes’ surface area would be increased. To overcome this deficiency of
surface area, we have spin-coated ZnO NPs on top of NWs. For a single layer of NPs (Figure 2),
besides the formation of a topping layer, it can be seen that nearly all of the NPs fill the interstices
between the NWs, yielding a combined structure of NWs and NPs. In case of double layers, NPs were
detached on top of the NWs. Some NPs were partially penetrated and dispersed between the gaps of
nanowires, but a large portion of NPs remained coated on the surface of the nanowire arrays.
However, in case of triple layers, NPs were sitting on the top of the nanowire arrays without any
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infiltration between the gaps of NWs except for those that dispersed during the first and second layer.
As a result of this infiltration, a thick layer of NPs is built on the surface of NWs (Figure 4, Schematic),
which reduces the penetration (diffusion) of electrons from NPs to NWs and increases the
trapping/detrapping events. The average thickness of the nanoparticles coating measured by Image
J software (Figure 5, Histogram) was 90, 172, and 275 nm for the single, double, and triple layers,
respectively.
Figure 4. Schematic representation of photoelectrodes made from nanowires (NWs), NWs+a single
layer of nanoparticles(NPs), NWs+a double layer of NPs, and NWs+ atriple layer of NPs.
Figure 5. Histogram of increase in length (thickness) with different coating layers.
3.3. Optical Analysis of Dye/ZnO Anodes
In Figure 6, the absorption spectra of dye/ZnO NWs, NWs+a single layer of NPs, NWs+a double
layer of NPs, and NWs+a triple layer of NPs are shown. It is observed that all the NWs and NWs+NPs
electrodes present an absorption peak at 520 nm. These peaks at 520 nm in all the electrodes are due
to a visible 4d-π* metal-to-ligand charge transfer (MLCT) in N719 dye [32]. Due to the presence of
coupling strength between the surface of ZnO NWs and NWs+NPs electrodes and excited dye, these
absorption peaks are slightly blue shifted. The different NPs layers on the top of NWs will provide a
Micromachines 2019, 10, 819 7 of 11
large surface area for dye loading, and hence improve the light harvesting capability of
photoelectrodes. It is clear from the absorption spectra (Figure 6) that the dye adsorption capacity of
NWs and NWs+NPs films with different layers of NPs is rated in the following order, from high to
low: the single layer of a NP compound nanostructure (NWs+a single layer of NPs), nanowires
(NWs), a double layer of a NP compound structure (NWs+a double layer of NPs), and a triple layer
of a NP compound structure (NWs+a triple layer of NPs). It is evident from the spectra that the single
layer of a NP (NWs+a single layer of NPs) compound nanostructure has the highest dye adsorption
capacity, because such a configuration contributes more surface area for dye molecules. Hence, as a
result, the current density (JSC) and overall light-to-energy conversion efficiency would increase. The
dye adsorption capacity of NWs is less than NWs+a single layer of NPs due to the lower surface area.
The other two samples, i.e., NWs+a double layer of NPs and NWs+a triple layer of NPs, show lesser
dye adsorption capacity because of the presence of double and triple layers of NPs on the top of the
NWs. Since the dye adsorption becomes weaker as the thickness of the layers increases, a thicker
layer blocks the complete infiltration of dye into the whole sample. Chang et al. and other researchers
proposed that insufficient film thickness leads to a low interfacial surface area, whereas an overly
thick film aggravates unnecessary charge recombination and poses more constraint on mass transfer
[33–36]. As a result, a photoanode that is too thin or too thick results in lower conversion efficiency.
Furthermore, it also causes higher electron transport resistance and increases the recombination of
electrons with 𝐼 on the ZnO surface, resulting in smaller open circuit voltage and efficiency.
Figure 6. Optical absorbance of N719 dye adsorbed on ZnO compound nanstructures.
3.4. Current Voltage (I–V) Analysis of DSSCs
Figure 7 shows the photoelectric characteristics for NWs, NWs+a single layer of NPs, NWs+a
double layer of NPs, and NWs+a triple layer of NP compound structure-based solar cells. The
parameters measured from I–V curves for thebest cells prepared from different coating layers of NPs
on ZnO nanowires are listed in Table 1. Under illumination, the NWs cell show aJSC of 2.64 mA/cm2,
fill factor (FF) of 0.74, VOC of 0.72 V, and η of 1.43 %.The NWs photoelectrodes have insufficient
internal surface area that results in lower dye loading and lightharvesting [20,21,37,38].The NWs+a
single layer of NPs compound structure shows aJSCof 3.02 mA/cm2, FF of 0.76, VOCof 0.74 V, and ηof
2.28%. The JSC, η, and overall performance obtained from the NWs+a single layer of NPs-based DSSC
Micromachines 2019, 10, 819 8 of 11
are substantially increased compared with those of NWs cells alone. The significant enhancement in
these results was possibly caused by the superior lightharvesting of the NWs+a single layer of NPs
DSSC, in which NPs provide the higher specific surface area for more dye anchoring and the NWs
provide an effective pathway for rapid electron transport [27,28,39]. These results from the NWs and
NWs+a single layer of NPs DSSCs closely matched with the results obtained from NWs, NRs, and
nanotips [21,24,28,29,40–42], and the results of NWs+a single layer of NPs compound nanostructure
show a considerable agreement with the results reported by other researchers listed in Table 2 for
comparison [27,43,44–48]. On the other hand, the other samples of NWs+a double layer of NPs and
NWs+a triple layer of NPs show worse performance; i.e.,JSC decreases from 3.02 to 2.11 mA/cm2 and
η decreases from 2.28% to 0.86 % (Figure 7, Table 1) compared withthose of NWs+a single layer of
NPs. This is due to the double and triple layer of nanoparticles on the top of nanowires, because most
of the nanoparticles are sitting on the top of nanowireswithout any infiltration, where the resulting
nanoparticle–nanowire contact area is minimized. It is worth noting that nanoparticle–nanowire and
nanoparticle–nanoparticle contact areas are also important [27]. From Figure 4, the interface between
two phases can be seen clearly, and the nanoparticles do not fill the interstitial voids after coating
double and triple layers. The morphology obtained from double and triple coating layers—the thick
layers of nanoparticles—forms a bottleneck to electron transport, because all the current from a thick
layer of nanoparticles must pass through the nanowires to reach the electrode. Moreover, this thick
layer also causes higher electron transport resistance and increases the recombination of electron with
𝐼 on the ZnO surface, resulting in smaller Voc and η values. The cells fabricated from double and
triple layers of NP photoelectrodes have shown low efficiency compared with their NWs/NWs+a
single layer of NPs-based DSSCs counterparts. This decrease in η is due to the following reasons.First,
electron transfer from NP thick-layer electrodes is proposed to occur by a series of hopping events,
which shows charge recombination and a non-exponential current, thereby slowing down excellent
charge transport [31]. Second, the transport of electrons in the NPs film undergoes multiple trapping
and detrapping processes. In addition, grain boundaries and mid gap states increased because of the
thicker layers of NPs on the top of NWs, which results in a slow electron transport rate [49]. Third,
an obvious drawback of the use of a double or triple layer of NPs on the top of NWs is that the
thickness increases, whereas an overly thick film aggravates unwanted charge recombination and
poses more constraints on mass transfer [33,34]. Thus, from the above discussion, we can infer that
the appropriate content of NPs incorporation onto the NWs can promote the dye adsorption,
transport the electrons, decrease the recombination of charge, and thereby increase the cells’
performance.
Table 1. Parameters of ZnO nanostructured-based dye-sensitized solar cells(DSSCs).
Short-Circuit Photocurrent Open-Circuit Fill Factor
Samples 𝜼 (%)
Density 𝑱sc (mA/cm2) Voltage 𝑽oc(V) (FF)
NWs 2.64 ± 0.021 0.72 ± 0.020 0.74 ± 0.025 1.43 ± 0.015
NWs + single of NPs 3.02 ± 0.010 0.74 ± 0.015 0.76 ± 0.020 2.28 ± 0.011
NWs + double of NPs 2.22 ± 0.005 0.69 ± 0.012 0.62 ± 0.005 0.93 ± 0.017
NWs + triple of NPs 2.11 ± 0.011 0.68 ± 0.010 0.58 ± 0.005 0.86 ± 0.001
Table 2. Comparison of performance parameters of DSSCs.
Short-Circuit
Open-Circuit Fill Factor
Samples Photocurrent Density 𝑱sc 𝜼 (%)
Voltage 𝑽oc (V) (FF)
(mA/cm2)
ZnO NW–NP hybrid cell [27] 3.00 0.77 0.65 1.3
ZnO NW [44] 2.5 0.44 0.47 0.45
ZnO NW–NP composite [44] 8.33 0.58 0.58 2.77
ZnO NW [45] 4.55 0.60 0.41 1.16
ZnO NW–NP hybrid cell [45] 15.16 0.61 0.46 4.24
ZnO NW [46] 2.52 0.53 0.37 0.49
ZnO NW–NP hierarchical [46] 5.4 0.62 0.60 2.03
ZnO NR–NP hybrid cell [47] 5.39 0.52 0.57 1.6
ZnO NR–NP hybrid cell [48] 4.57 0.45 0.34 0.69
Micromachines 2019, 10, 819 9 of 11
Figure 7. J–V characteristics for ZnO compound nanostructures.
4. Conclusions
In summary, ZnO NWs and compound nanostructures of ZnO NWs+NPs with different coating
layers of NPs on top of NWs were fabricated for the application of DSSCs. The transportation of
electrons is high in compound nanostructures (NWs + NPs), and ZnO NPs filling the gaps between
the ZnO NWs offers a high internal surface area for loading the dye and lightharvesting. The overall
maximum efficiency of 2.28% for NWs+a single layer of NPs-based DSSCs was achieved with FF, VOC,
JSC values of 0.76, 0.74V, and 3.02 mA/cm2, respectively, which is 165% higher than that of their other
counterparts. The improved performance was obtained due to the large surface area and light
harvesting of compound nanostructures.
Author Contributions: Conceptualization, M.S.; methodology, W.A.F.; formal analysis, N.A.; investigation,
M.N.A.; resources, S.U.R.; writing—original draft preparation, M.S. and M.I.K.; writing—review and editing,
M.K., M.A. and M.I.; project administration, W.A.F.; funding acquisition, M.A.A.
Funding: The authors would like to extend their sincere appreciation to the Deanship of Scientific Research at
King Saud University for its funding of this research through the Research Group Project no. RG-1435-059.
Conflicts of Interest: The authors declare no conflict of interest.
References
1. O’Regan, B.; Grätzel, M. A low-cost, high-efficiency solar cell based on dye-sensitized colloidal TiO2 films.
Nature 1991, 353, 353–737.
2. Grätzel, M. Photoelectrochemical cells. Nature 2001, 5, 414–338.
3. Liu, J.; Cao, G.Z.; Yang, Z.; Wang, D.; Dubois, D.; Zhou, X.; Graff, G.L.; Pederson, L.R.; Zhang, J.-G. Oriented
nanostructures for energy conversion and storage. Chem. Sus. Chem. 2008, 1, 258–265.
4. Goetzberger, A.; Hebling, C. Photovoltaic materials, past, present, future. Sol. Energy Mater. Sol. Cells 2000,
62, 13546–13551.
5. Goetzberger, A.; Hebling, C. Schock, H.W. Photovoltaic materials, history, status and outlook. Mater. Sci.
Eng. R Rep. 2003, 1, 40–46.
6. Bagnall, D.M.; B, M. Photovoltaic technologies. Energy Pol. 2008, 36, 4390–4396.
Micromachines 2019, 10, 819 10 of 11
7. Green, M.A. Recent developments in photovoltaics. Sol. Energy 2004, 76, 3–8.
8. Oliver, M.; Jackson, T. The market for solar photovoltaics. Energy Pol. 1999, 27, 371–385.
9. Lieber, C.M.; Wang, Z.L. Functional nanowires. MRS Bull. 2007, 32, 99–108.
10. Sattler, K. Handbook of Nanophysics: Nanotubes and Nanowires; CRC: Boca raton, FL, USA, 2011.
11. Wang, Z. Nanowires and Nanobelts: Materials Properties and Devices: Volume 2: Nanowires and
Nanobelts of Functional Materials; Springer–Verlag: Berlin, Germany, 2005.
12. Pan, Z.W.; Dai, Z.R.; Wang, Z.L. Nanobelts of semiconducting oxides. Science 2001, 291, 1947–1949.
13. Wang, Z. Oxide nanobelts and nanowires—growth, properties and applications. J. Nanosci. Nanotechnol.
2008, 8, 27–55.
14. Feldheim, D.; Foss, C. Metal Nanoparticles: Synthesis, Characterization and Applications; CRC: Boca raton, FL,
USA,2002.
15. Sugimoto, T. Fine Particles: Synthesis, Characterization and Mechanisms of Growth; CRC: Boca raton, FL,
USA,2000.
16. Grätzel, M. Sol-gel processed TiO2 films for photovoltaic applications. J. Sol–Gel Sci. Technol. 2001, 22, 7–13.
17. Saito, R.; Dresselhaus, G.; Dresselhaus, M. Physical Properties of Carbon Nanotubes; Imperial College Press:
London, UK, 1999.
18. Baughman, R.H.; Zakhidov, A.A.; de Heer, W.A. Carbon nanotubes–the route toward applications. Science
2002, 297, 787–792.
19. Grätzel, M. Solar energy conversion by dye-sensitized photovoltaic cells. Inorg. Chem. 2005, 44, 6841–6851.
20. Law, M.; Greene, L.E.; Johnson, J.C.; Saykally, R.; Yang, P.D. Nanowire dye-sensitized solar cells. Nat.
Mater. 2005, 4, 455–459.
21. Baxter, J.B.; Aydil, E.S. Nanowire-based dye-sensitized solar cells. Appl. Phys. Lett. 2005, 86, 053114–053117.
22. Paulose, M.; Shankar, K.; Varghese, O.K.; Mor, G.K.; Grimes, C.A. Application of highly-ordered TiO2
nanotube-arrays in heterojunction dye-sensitized solar cells.J. Phys. D 2006, 39, 2498–2503.
23. Wang, H.; Yip, C.T.; Cheung, K.Y.; Djurisic, A.B.; Xie, M.H.; Leung, Y.H.; Chan, W.K. Titania-nanotube-
array-based photovoltaic cells. Appl. Phys. Lett. 2006, 89, 023508–023510.
24. Jiang, C.Y.; Sun, X.W.; Lo, G.Q.; Kwong, D.L.; Wang, J.X. Improved dye-sensitized solar cells with a ZnO-
nanoflower photoanode. Appl. Phys. Lett. 2007, 90, 263501–263503.
25. Cheng, H.M.; Chiu, W.H.; Lee, C.H.; Tsai, S.Y.; Hsieh, W.F. Formation of branched ZnO nanowires from
solvothermal method and dye-sensitized solar cells applications. J. Phys. Chem. C 2008, 112, 16359–16364.
26. Chen, W.; Zhang, H.; Hsing, I.M.; Yang, S. A new photoanode architecture of dye sensitized solar cell based
on ZnO nanotetrapods with no need for calcination. Electrochem. Commun. 2009, 11, 1057–1060.
27. Baxter, J.B.; Aydil, E.S.Dye-sensitized solar cells based on semiconductor morphologies with ZnO
nanowires. Energy Mater. Sol. Cells 2006, 90, 607–622.
28. Ku, C.H.; Wu, J.J. Electron transport properties in ZnO nanowire array/noparticle composite dye-sensitized
solar cells. Appl. Phys. Lett. 2007, 91, 093117.
29. Ku, C.H.; Wu, J.J. Dye-sensitized solar cells based on nanoparticle-decorated ZnO/TiO2 core/shell nanorod
arrays, Appl. Phys. Lett. 2007, 91, 093117–093123.
30. Law, M.; Greene, L.E.; Radenovic, A.; Kuykendall TLiphardt, J.; Yang, P.D. ZnO−Al2O3 and ZnO−TiO2
Core−Shell Nanowire Dye-Sensitized Solar Cell. J. Phys. Chem. B 2006, 110, 22652.
31. Saleem, M.; Fang, L.; Ahmad, M.A.; Raza, R.; Wu, F.; Li, W.J.; Xu, C.L.; Hu, L.; Xue, S.J. Synthesis,
Characteristic and Appliction of ZnO Nanowires in dye-sensitized solar cells via Water Bath method, Nano
2014, 9, 1450061–1450068.
32. Saleem, M.; Fang, L.; Shaukat, S.F.; Ahmad, M.A.; Raza, R.; Akhtar, M.N.; Jamil, A.; Aslam S.; Abbas, G.
Structural and photovoltaic characteristics of hierarchical ZnO nanostructures electrodes. Appl. Surf. Sci.
2015, 334, 145–150.
33. Wang, Z.S.; Kawauchi, H.; Kashima, T.; Arakawa, H. Significant influence of TiO2 photoelectrode
morphology on the energy conversion efficiency of N719 dye–sensitized solar cell. Coord. Chem. Rev. 2004,
248, 1381–1389.
34. Tan, B.; Wu, Y.Y. Dye–sensitized solar cells based on anatase TiO2 nanoparticle/nanowire composites. J.
Phys. Chem. B 2006, 110, 15932–15938.
35. Lee, B.; Hwang, D.K.; Guo, P.; Ho, S.T.; Buchholtz, D.B.; Wang, C.Y.; Chang, R.P.H. Materials, interfaces,
and photon confinement in dye–sensitized solar cells. J. Phys. Chem. B 2010, 114, 14582–14591.
Micromachines 2019, 10, 819 11 of 11
36. Hsu, C.P.; Lee, K.M.; Huang, J.T.W.; Lin, C.Y.; Lee, C.H.; Wang, L.P.; Tsai, S.Y.; Ho, K.C. EIS analysis on
low temperature fabrication of TiO2 porous films for dyesensitized solar cells. Electrochim. Acta 2008, 53,
7514–7522.
37. Suri, P.; Mehra, R.M. Effect of electrolytes on the photovoltaic performance of a hybrid dye sensitized ZnO
solar cell. Sol. Energy Mater. Sol. Cells 2007, 91, 518–524.
38. Sheng, X.; Zhao, Y.; Zhai, J.; Jiang, L.; Zhu, D. Electro-hydrodynamic fabrication of ZnO-based dye
sensitized solar cells. Appl. Phys. A 2007, 87, 715–719.
39. Wang, Y.; Sun, Y.; Li, K. Dye-sensitized solar cells based on oriented ZnO nanowire-covered TiO2
nanoparticle composite film electrodes. Mater. Lett. 2009, 63, 1102–1104.
40. Pasquier, A.D.; Chen, H.; Lu, Y. Dye sensitized solar cells using well-aligned zinc oxide nanotip arrays.
Appl. Phys. Lett. 2006, 89, 253513–253515.
41. Baxter, J.B.; Walker, A.M.; van Ommering, K.; Aydil, E.S. Synthesis and characterization of ZnO nanowires
and their integration into dye-sensitized solar cells. Nanotechnology 2006, 17, S304–S312.
42. Gao, H.; Fang, G.; Wang, M.; Liu, N.; Yuan, L.; Li, C.; Ai, L.; Zhang, J.; Zhou, C.; Wu, S.; Zhao, X. The effect
of growth conditions on the properties of ZnO nanorod dye-sensitized solar cells. Mater. Res. Bull. 2008, 43,
3345–3351.
43. Zhu, Y.F.; Shen, W.Z. Synthesis of ZnO compound nanostructures via a chemical route for photovoltaic
applications, Appl. Phys. Lett. 2010, 256, 7472–7476.
44. Ku, C.H., Wu, J.J. Chemical bath deposition of ZnO nanowire–nanoparticle composite electrodes for use in
dye-sensitized solar cells. Nanotechnology 2007, 18, 505706.
45. Yodyingyong, S.; Zhang, Q.; Park, K.; Dandeneau, C.S.; Zhou, X.; Triampo, D.; Cao, G. ZnO nanoparticles
and nanowire array hybrid photoanodes for dye-sensitized solar cells. Appl. Phys. Lett. 2010, 96, 073115.
46. Victoire–Marie, G.; Thierry, P. From nanowires to hierarchical structures of template-free electrodeposited
ZnO for efficient dye-sensitized solar cells, Energy Environ. Sci. 2011, 4, 297.
47. Haller, S.; Suguira, T.; Lincot, D.; Yoshida, T. Design of a hierarchical structure of ZnO by electrochemistry
for ZnO-based dye-sensitized solar cells. Phys. Status Solidi A 2010, 207, 2252–2257.
48. Urgessa, Z.N.; Ruessa, R.; Djiokap, S.R.T.; Botha, J.R.; Schlettwein, D. Effect of morphology and surface
treatment on the performance of ZnO nanorod-based dye-sensitized solar cells. J. Alloys Compd. 2019, 798,
249–256.
49. Kopidakis, N.; Schiff, E.A.; Park, N.G.; van de Lagemaat, J.; Frank, A.J. Ambipolar Diffusion of
Photocarriers in Electrolyte-Filled, Nanoporous TiO2. J. Phys. Chem. B 2000, 104, 3930–3936.
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