Accepted Manuscript

Hydrothermally synthesized fluorescent Zn2SnO4 nanoparticles for dye sensitized

solar cells

Partha Pratim Das, Anurag Roy, Shruti Agarkar, Parukuttyamma Sujatha Devi

PII: S0143-7208(17)32049-1
DOI: 10.1016/j.dyepig.2017.12.066
Reference: DYPI 6472

To appear in: Dyes and Pigments

Received Date: 29 September 2017

Revised Date: 18 December 2017
Accepted Date: 30 December 2017

Please cite this article as: Das PP, Roy A, Agarkar S, Devi PS, Hydrothermally synthesized fluorescent
Zn2SnO4 nanoparticles for dye sensitized solar cells, Dyes and Pigments (2018), doi: 10.1016/
j.dyepig.2017.12.066.

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 ACCEPTED MANUSCRIPT
Hydrothermally Synthesized Fluorescent Zn2SnO4 Nanoparticles for Dye

Sensitized Solar Cells

⃰
Partha Pratim Das, Anurag Roy, Shruti Agarkar, and Parukuttyamma Sujatha Devi

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Graphical Abstract

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Hydrothermally synthesized Zn2SnO4 nanoparticles possessing UV emission exhibited

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resonance energy transfer with N719 and exhibited an improved DSSC efficiency of 2.56%.
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 ACCEPTED MANUSCRIPT

Hydrothermally synthesized fluorescent Zn2SnO4 nanoparticles for dye

sensitized solar cells

Partha Pratim Dasa,b, Anurag Roya, Shruti Agarkar c and Parukuttyamma Sujatha Devia *
a
Sensor and Actuator Division, CSIR-Central Glass and Ceramic Research Institute, Kolkata

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700032, India.
b
Presently at Crystallography Lab, Department of Earth System Sciences, Yonsei University,

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Yonseiro-50, Seoul-03722, Korea.
c
Physical and Materials Chemistry Division, CSIR-National Chemical Laboratory, Pune 411

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008, India. £Presently at School of Chemistry and Biochemistry, Georgia Institute of
Technology, Atlanta, GA 30332

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*Email: psujathadevi@cgcri.res.in , psujathadevi@gmail.com
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ABSTRACT
In this work, we have investigated the interaction of hydrothermally synthesized Zn2SnO4
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(ZTO) nanoparticles (NPs) with two different commercial photo sensitizers such as N719 and
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N3 dye molecules and studied their performance in dye sensitized solar cells (DSSC).
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Interestingly, the ZTO NPs exhibited band edge emission in the mid UVA region and as a

result possibility of enhanced light harvesting in the terminal UVA region was anticipated in
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the device due to the efficient energy transfer observed in case of the sensitizer N719 than

N3. The dye sensitization property has been found to be higher for the N3 dye molecules than
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the N719 dye molecules as based on the time dependent dye loading study. The devices
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fabricated with ZTO-N719 exhibited improved photovoltaic performance compared to the

ZTO-N3 based devices exhibiting an overall conversion efficiency of 2.56% by the former

compared to the later (1.90%) under 1SUN 1.5AM illumination and sensitization for 12h.

Keywords: Zinc stannate, optical properties, photo-physical interactions, dye loading,

DSSC
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1. Introduction

Recent developments have projected Dye-sensitized solar cells (DSSCs) as a promising

technology for the solar energy conversion due to its cost effective fabrication techniques and

eco-friendliness [1]. One of the most crucial challenges faced in DSSC is the lack of efficient

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harvesting of photons in the whole solar spectrum for high conversion [2, 3]. Two principal

components of DSSC, the photosensitizing dye molecule and the semiconducting metal oxide

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nanoparticles are mainly responsible for the conversion of solar energy to electrical energy.

Several approaches have been implemented to enhance the overall efficiency of DSSC

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devices such as co-sensitization with compatible dyes, development of new sensitizers,

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quantum-dots cascade cells, tandem cells or by adding light scattering and embedding
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plasmonic structure [4-8]. In addition to the usual approaches as mentioned earlier, an

alternative approach to enhance the cell efficiency through Forster resonance energy transfer
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(FRET) in which non-radiative energy transfer takes place between two molecules of the

device coupled through donor-acceptor pairing has also been looked into for possible
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enhanced light absorption [9-13]. Few reports are available on FRET-based DSSC’s where
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the basic objective was to design and identify new donor-acceptor pairs [14, 15]. Amongst
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the available reports, exploration of the energy emitted by the semiconductor materials used

as photoanode for the excitation of the surface adsorbed sensitizers is quite significant and
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interesting [16,17]. Presently Zn2SnO4 (ZTO) has been proved as a potential candidate for
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dye-sensitized solar cells (DSSCs) for its high electron mobility, high electrical

conductivity,sufficient thermodynamic stability in addition to its interesting optical properties

[18-24].In our earlier publications, we have highlighted the ability of ZTO in exhibiting

higher Voc and established the enhanced stability of the same in the environment of

sensitizers of different acidity such as N3, N719 and Eosin Y dyes [22, 23]. Based on the

time dependent absorption studies, systematic spectroscopic studies and water contact angle

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measurements, we were able to establish the effect of anchoring groups in controlling the dye

loading behaviour where the calculated dye loading ability of ZTO followed the order N3 >

N719 >> Eosin Y [23]. Effective dye loading and chemical stability between the photoanode

materials and the sensitizers are two important factors to be considered during designing the

device. Therefore, we have selected N3 and N719 as sensitizers in this present study. In

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addition, we have synthesized nanosized ZTO by a hydrothermal route which absorbs high

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energy photon of the terminal UVA region and exhibits mid UVA emission. This could act as

a donor by transferring energy to the acceptor dye molecules and thereby extend the

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absorption region of the sensitizer beyond the UVA absorption limit without sacrificing the

usual performance in the visible region. Such system could make the DSSC device capable of

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harvesting additional solar light of higher energy and reduce the chances of recombination.
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Lowering recombination is also crucial for a DSSC device for performing better. Therefore,
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based on several interesting photo-physical studies, we have investigated the suitability of

energy transfer between the synthesized fluorescent ZTO NPs and the most common
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sensitizers N719 and N3.

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2. Experimental Procedure

2.1. Materials
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Zinc chloride [ZnCl2, 98%], triethylamine (TEA) [99% GR] and Ethylene glycol [99% GR]
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from Merck, India, Tin (IV) chloride pentahydrate [SnCl4, 5H2O, 98%] from Sigma Aldrich,
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were used for the synthesis. All the chemicals have been used as received without further

purification.

2.2. Synthesis

For a typical batch preparation, 0.525 g of Zinc chloride and 0.675 g of Tin (IV) chloride

pentahydrate were dissolved in 50 ml of water/ethylene glycol (volume ratio 1:1) under

constant stirring on a magnetic stirrer followed by the drop-wise addition of 25 ml of 1.3 M

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triethylamine (TEA) to the solution. The mixture was further stirred continuously for 2 hours

for forming white slurry. The white slurry was transferred into a teflon-lined autoclave and

kept at 175 ± 5oC for 24 hours followed by natural cooling. The precipitate was further

washed thoroughly with distilled water for several times to remove the excess amine and

dried under IR lamp at ~80oC and finally annealed at 500oC for 2 hours to convert to the final

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oxide of right composition and purity.

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2.3. Materials characterization

Thermo gravimetric analysis (TGA) of the as prepared powder was carried out from RT to

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1000°C with a heating rate of 10°C/min on a NETZSCH 449C simultaneous thermal analyser

to understand the stability of the sample. The annealed powder was characterized by powder

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X-ray diffraction (XRD) analysis on a X’pert pro MPD XRD of PAN analytical with Cu Kα
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radiation (λ=1.5406 Å) for phase confirmation. The size and morphology of the sample was
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monitored using transmission electron microscopy (TEM) which was carried out on a Tecnai

G2 30ST (FEI) high resolution transmission electron microscope operating at 300 kV. The
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dynamic light scattering (DLS) measurement for understanding the particle size distribution
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was performed on a Horiba (SZ-100) analyzer. X-ray photoemission spectroscopy (XPS)

measurements were carried out on PHI 5000 Versa probe II scanning XPS microprobe
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(ULVAC-PHI, U.S.). All spectra were recorded with monochromatic Al Kα (hν = 1486.6 eV)
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radiations with a total resolution of about 0.7 eV and a beam size of 100 µm. Fourier
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transform infrared (FTIR) absorption spectra of the samples were recorded on a Nicolet 380

FTIR spectrometer. Raman spectra were recorded using a RenishawInVia Reflex micro

Raman spectrometer using argon ion (514 nm) laser. The data was collected with a resolution

of 1 cm-1. The absorbance spectrum of the ZTO nanoparticles has been measured using an

UV-Vis-NIR spectrometer (Shimadzu UV-3600). The absorption spectra of the dyes and the

unadsorbed dyes with time have also been measured as above. The room temperature

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emission spectra (PL) have been measured on a steady state spectrofluorometer (QM-40,

Photon Technology International, PTI) using a Xenon lamp as an excitation source. The

excitation wavelength was fixed at 320 nm and a band pass of 5 nm was used in all the cases.

Fluorescence quantum yield of the ZTO solution in presence and absence of the

photosensitizers have been measured on the same steady-state spectrofluorometer using an

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integrating sphere. The I-V characteristics of ZTO films before and after dye loading were

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measured using an Agilent two-channel precision source and measurement unit (model no.

B2902A). The surface wettability of the dye loaded ZTO film surface was determined by

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measuring the water contact angles on a drop shape analyzer (Kruss DSA25) using Young’s

equation (sessile drop method) where the volume of each drop was fixed at 5 mL and the rate

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of dosing was 500 mL min-1. A charge-coupled device (CCD) camera equipped with the
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instrument was used for capturing the image.
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2.4. Fabrication of the dye-sensitized solar cell

The ZTO films were prepared by the doctor blade method on FTO glass (7 Ω/ cm2) and
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annealed further at 450oC for 1 h. The measured thickness of the films was ~5µm. A 0.5mM
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methanolic solution of N719 and N3 were used as light sensitizers. The J-V characteristics of

the fabricated devices have been measured using a solar simulator (Newport) at 100 mW/cm2
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(1 sun AM 1.5). A standard silicon solar cell (SER NO. 189/PVM351) from Newport, U.S.
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was executed as the reference cell. The data presented are an average of measurements taken
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on five different devices for each sample. The details of the cell fabrication are reported

elsewhere [25].

3. Results and Discussion

3.1. Structural and micro structural analysis

In order to understand the thermal decomposition behaviour thermogravimetric analysis of

the as-prepared powder has been carried out in the range of room temperature to 1000°C as

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exhibited in Fig. S1(a). The observed weight loss upto around 450°C is due to the liberation

of surface adsorbed water and NH4+ ions. The weight loss was quite insignificant beyond

450°C confirming the stable nature of the sample upto minimum 1000°C. The sample

obtained after annealing was characterized for phase purity with X-ray diffraction (XRD)

study as shown in Fig. 1(a). All the diffraction peaks can be indexed to match the cubic

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crystal structure of Zn2SnO4. The calculated lattice parameter, 8.681 Å, matches well with

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that reported for Zn2SnO4 (JCPDS card no: 74-2184, lattice parameter: 8.650Å). The

crystallite size of the sample is ~10.82 nm as calculated from the well-known Scherer

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equation unequivocally suggests the particles formed are in the nanometer order. We have

also verified the phase purity of the as prepared sample calcined at an elevated temperature of

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900 °C by X-ray diffraction study. Similar diffraction pattern of the same corroborates the
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TGA analysis regarding the stability of the formed material. In order to monitor the size,
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distribution and morphology and to confirm the purity and crystallinity of the sample,

Transmission Electron Microscopic investigations have been carried out as shown in the
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representative TEM micrographs in Fig. 1(b-d). The bright field image (Fig. 1b) confirms the
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nanocrystalline nature of majority of the separated particles having an average size of ~7 nm

with a polydispersity index less than 0.2 nm which further indicates the monodispersity
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shown in the histogram plot (Fig. 1b inset) . A significant weak interconnection among two-
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three distinct particles is an obvious outcome of the sample synthesized hydrothermally in

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water/ethylene glycol (volume ratio 1:1) medium without using any surfactant or matrix. The

lattice fringes in high resolution TEM image (Fig. 1c) corresponds to the (111) reflection

with a d spacing of 5.01Å which confirms the single crystalline nature of the sample. Inset

shows the corresponding fast fourier transform (FFT) of the high resolution TEM in

particular. The corresponding selected area electron diffraction (SAED) pattern in Fig. 1(d)

has been indexed to the (222), (220) and (511) planes of ZTO. The small spots with distinct

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ring in the SAED pattern again refer the nano-poly crystalline nature of the nanoparticle

sample. The particle size distribution profile of the sample is further verified by DLS

technique and has been exhibited as Fig. S1(b). The DLS measurement demonstrates a

comprehensively mono dispersive distribution of the particles having average hydrodynamic

diameter of ~15 nm which corroborates the previous inferences from X-ray diffraction data

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and TEM analysis regarding the size and distribution of the particles of the studied sample.

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The average particle sizes of the studied ZTO determined based on the aforementioned XRD,

TEM and DLS methods are summarized in Table T1 (ESI).

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3.2. Optical properties of the ZTO samples

In order to further understand the functional nature the sample, the synthesized ZTO

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nanoparticles have been characterised by FTIR and Raman spectroscopy as shown in Fig. 2(a
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and b). Fig. 2(a) exhibit the FTIR spectra of the studied ZTO sample (i.e., annealed at 500;

black curve) and the sample annealed at an elevated temperature of 900oC (red curve). The
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broad band in Fig. 2(a) centered at ~3435 cm-1 corresponds to the stretching vibration of O-H
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bonds of adsorbed water onto the ZTO surface which disappeared by annealing the sample at
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900oC. The sharp and intense band appeared at 572 cm-1 assigned to the characteristics

vibration band for Zn-O-Sn of the inverse spinel ZTO and further supports the XRD results
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of the formation of phase pure ZTO by the hydrothermal synthesis [19, 20]. Interestingly no
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shift in this vibration band even after annealing the sample at 900°C again suggests the
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stability of Zn-O-Sn bond of cubic Zn2SnO4 at this higher temperature. The Raman spectrum

of the studied ZTO sample collected at room temperature is displayed in Fig. 2(b). The broad

feature of the spectrum signifies the nanocrystalline nature of the synthesized particles which

further corroborates the TEM analysis. Upon deconvolution, the main broad Raman active

band exhibits two distinct peaks. The dominant band at 670 cm-1 can be ascribed to the

characteristic A1g symmetry emerged due to the symmetric stretching of the Zn-O bonds in

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the ZnO4 tetrahedra of the inverse spinel ZTO [19, 20]. It was worth noting the unusual and

suppressed Raman phonon band appeared at ~626 cm-1 in the sample. As reported earlier, this

additional band has been assigned to the Raman active vibration mode of the Sn-O bonds of

A1g symmetry in the SnO4 tetrahedra originated due to the redistribution of Sn and Zn cations

over the (A) and [B] lattice sites of the spinel ZTO crystal[26]. Interestingly in this case the

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band appeared without applying any high temperature or imposing any high pressure or by

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irradiation of any high energy sources [26]. This kind of a structural disorder of ZTO

nanoparticles may further modify its band energy gap, optical and electrical property which

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could influence the photovoltaic parameters of the fabricated DSSCs device [24, 25]. The

room temperature UV-Vis absorption and diffuse reflectance spectrum of the ZTO have been

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measured separately and are displayed in Fig. 2(c). The absorption spectrum for the intrinsic
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band gap transition was observed which started ascending ~350 nm. The steep rise of the
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absorption spectrum unambiguously predicts that this transition does not originate from an

impurity level or any other structural defect. In support, the diffuse reflectance spectra have
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also been performed. Following the Tauc’s equation, αhυ = A (hυ – Eg)1/2, where α, υ, h
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corresponds to the absorption coefficient, frequency and Planck’s constant respectively, the

(αhυ)2 versus photo energy (hυ) have been plotted and shown in inset of Fig. 2(c).The
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estimated band gap (Eg) from the intersection of the extrapolated linear portion of the
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absorption edge is ~3.52 eV. Moreover, the synthesized ZTO nanoparticles, exhibited a room
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temperature emission with a peak maximum around 355 nm with respect to excitation at 320

nm is displayed as Fig. 2(d). This attributes to the near band emission (NBE) of the ZTO

nanoparticles [26, 27]. In order to establish this we have studied the excitation dependent

emission properties of the synthesized nanoparticles with varying the excitation wavelength

from 300 nm to 340 nm, inset of Fig. 2(d). The invariable nature of the emission spectrum

strengthens emission characteristic originating from band to band transition. In addition to the

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main band emission, very weak bands also appeared in the blue-green region around 400-500

nm attributing to the emissions from oxygen vacancy defects having energy levels in between

the valence and conduction band of the multication oxide [31,32]. The defect related

emissions are quite lower in intensity indeed compared to the band emission at the studied

excitation wavelengths.

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The X-ray photoelectron spectroscopy (XPS) measurements have been carried out to

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investigate the chemical composition at the surface and to ascertain the valence state of the

key elements Zn, Sn and O. The wide XPS spectra in Fig. 3(a) exhibited two strong peaks

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centered at 494.2 eV and 485.8 eV which can be assigned to the binding energies of Sn 3d3/2

and Sn 5d5/2 , respectively, splitted by spin orbit coupling whereas the strong peak centered

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at 25.2 eV (Fig. 3b) is due to the binding energy of Sn 4d. These are considered to be the
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characteristic binding energy of tetravalent Tin [33, 34]. Moreover, the Zn 2p spectra in Fig.
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3(c) centered at 1044.1 eV and 1020.9 eV can be attributed to the spin orbit split peaks of Zn

2p1/2 and Zn 2p3/2 , respectively, and can be assigned to the characteristics of divalent Zinc in
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the ZTO. On deconvolution, the asymmetric O 1s spectrum evolves into two components
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centered at 529.89 eV (O1 component) and 530.87 eV (O2 component) as shown in Fig. 2d.

The dominant O1 component is characteristics of O2- ions in the Zn-O-Sn metal oxide lattice
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framework whereas the O2 component at higher binding side may be associated with the
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presence of chemisorbed oxygen in the grain boundaries or the existence of hydroxyl group (-
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OH) due to adsorption of water (H2O) onto the surface of the ZTO during synthesis through

hydrothermal route which conclusively supports the FTIR data [33, 34].

3.3. Absorptions of the photo sensitizers N3 and N719

The absorption spectrum of sensitizers used in this study N719 and N3 dyes in ethanol in the

200-800 nm range is presented in Fig. S2(ESI). The sensitizers exhibits broad absorption

throughout the UV and Visible region having three absorption maxima at ~385 and ~395 nm

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for N719 and N3, respectively, mainly related to the metal to ligand charge transfer (MLCT)

of the dyes in Fig.S2 (ESI) and Table T2 (ESI). The strong absorption corresponding to

MLCT1 are almost in the overlap region of UVA and visible. The second broader absorptions

at λmax ~529 and ~534 nm, respectively for N719 and N3 are exclusively in the visible region

(MLCT2). On the contrary the highest energy sharp absorption with maxima at 314 nm for

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N3 and 310 nm for N719 which are actually doublet originate from the Π→Π* intraligand

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transition of the corresponding dyes [35, 36]. Therefore, both the dyes are considered to be

active predominantly in the visible region which is the major part of the solar irradiance

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spectrum as well [36].

3.4. Dye loading ability and stability of ZTO NPs

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The adsorption of N3 and N719 as a function of time on the synthesized ZTO NPs has also
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been verified by keeping the thickness of the photoanode films and the concentration of the
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dyes identical as mentioned in section 2.4. The absorption spectra of the residual solution of

N719 and N3 collected after the dye-impregnation different sensitization times has been
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represented as Fig. 4(a) and (b), respectively. The intensity of the absorption bands of N3
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decreased at a faster rate in the early adsorption process than N719. The rate of adsorption

decreased after 8h and got saturated after 12h for both the dyes as evidenced from the (C/C0)
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values shown in Fig. 4(c) and (d) where C0 and C represents the initial concentration of the dye
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and the concentration of the residual dye after adsorption at different time. The changes in surface
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characteristics of the ZTO films upon adsorption of N719 and N3 with time have further been

monitored by measuring the water contact angle as shown in Fig. 4(c) and (d) along with their

respective (C/C0) plots. The super hydrophilic surface of ZTO NP film having plenty of

hydroxyl group as evident from FTIR spectra in Fig. 2(a) exhibited a contact angle of ~ 5o

whereas the measured water contact angle of the same increased to ~41o and ~45o after

loading with N719 and N3, respectively, for 12h (Fig. 4(c) and (d), inset). A significant

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change in the contact angle after 12 h again confirms the saturation of dye adsorption in one

side and also indicates enough chemical stability of the ZTO film surface at this condition

[23]. Based on all these observations, we have decided to fix the maximum dye sensitization time

for 12h for cell testing along with an intermediate time of 8h. The consistently lower (C/C0) value

throughout the whole dye loading time scale and the higher contact angle i.e., more hydrophobic

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nature of the N3 adsorbed ZTO surface inevitably indicates a better loading of N3 by the

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hydrothermally synthesized ZTO NPs compared to N719. N3 having four free carboxylic acid

groups (-COOH) for anchoring gets advantage over N719 having only two anchoring groups

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(Fig.S2, ESI) [37].

4. Photo-physical interaction and energy transfer efficiency between ZTO -N719 and

ZTO -N3
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The observed I-V characteristics of ZTO films measured within a bias voltage of -40 V to +40
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V exhibited a reduction in photocurrent of 44% after loading N3 whereas this was around

60% for N719, thereby ensuring a better career transfer in the latter (Fig. 5). The UV active
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ZTO exhibited a much higher photocurrent upon UV illumination. This phenomenon

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admittedly indicates the energy transfer between ZTO-N719 and N3 which is more effective

for ZTO-N719 exceptionally in the UV region.

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As revealed from Fig. 2(d), the synthesized ZTO nanoparticles exhibited an emission
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spectrum in the mid UVA region with a band maximum at 355 nm. The RT emission as a
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consequence of the terminal UVA light excitation further brings forth the possibility of

energy transfer to the photosensitizers exclusively in the UVA region. Hereafter, the

excitation wavelength of the samples had been fixed at 320 nm for establishing the resonance

energy transfer dynamics in the studied systems.

Fig. 6(a) exhibits the room temperature emission spectra of ZTO nanoparticles recorded

under 320 nm light excitation and the absorbance spectra of the sensitizers N3 and N719 in

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ethanol originating from MLCT1. In the combined normalised absorption and emission

spectra (Fig. 6a) the shaded zones indicate the spectral overlap areas. The ash coloured zone

indicates the common overlap area of the two different sensitizers and ZTO. The pink and red

zone indicates the overlap area between ZTO-N719 and ZTO-N3, respectively. The overlap

area between the emission band of the nanosized ZTO and the absorption band of N719 is

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larger compared to that of ZTO and N3. In order to demonstrate the possibility of energy

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transfer from ZTO to N719, same the gradual quenching in emission of the donor molecules

have been studied by monitoring the emission spectra of the nanosized ZTO with increasing

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concentration of the acceptor sensitizers N719 and N3. The concentration of the sensitizers

had been increased from 1×10-7 M to 5×10-7 M with a regular increment of 1×10-7 M. It is

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worth mentioning rapid quenching of the emission of the donor ZTO got quenched quite
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rapidly in the event of the faster energy transfer to the acceptor N719 compared to N3 with
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increasing their concentrations. The quenching of the emission have been successively

depicted in Fig. 6(b) and (c) for N719 and N3, respectively. The ratio of the steady state
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emission intensity of the ZTO nanoparticles in absence (I0) and presence (I) of the acceptor
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sensitizers have been established in the Stern-Volmer (S-V) equation (equation 1). Here [S]

corresponds to the concentrations of the sensitizers and KSV represents the Stern-Volmer (S-
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V) constant [38]. The plot has been exhibited in Fig. 6(d).

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I0/I =1+ KSV[S] (1)

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Detailed derivation of the Stern-Volmer plots result the S-V constants (KSV) of 0.42×107 M-1

and 0.31×107 M-1, respectively, for the acceptor molecule N719 and N3 which asserts N719

as a faster quencher towards the synthesized ZTO compared to N3. The average energy

transfer efficiency (E) can further be calculated from equation 2 by measuring the

fluorescence intensity for the donor ZTO alone and in presence of the acceptor sensitizers.

E=1-(IZTO-Dye/ IZTO) (2)

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The calculated energy transfer efficiencies were found to be 55% for the acceptor N719 and a

much lower efficiency of 46% for N3. This establishes the superiority in the energy transfer

from the donor ZTO to the acceptor N719 compared to N3.

In order to explicit the dynamic nature of the quenching of emission of the donor by

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successful energy transfer towards acceptor sensitizers by ruling out the possibility of the

formation of any donor-acceptor complex in the ground state, the absorbance spectra of the

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acceptor dyes N719 and N3 have been measured on addition of the donor ZTO from a lower

to higher concentration where the concentration of the dyes are kept constant. In Fig. 7(a) and

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(c), respectively, the exclusive MLCT1 of 5× 10-7 M N719 and N3 in ethanol in presence of

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ZTO have been focused where the concentration of the ZTO have been successively increased
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from 0.1× 10-5 M depicted as (l) to 0.25× 10-5 M depicted as (h) in the figure. On the contrary

in Fig. 7(b) and (d), respectively, the MLCT2 of 5× 10-7 M N719 and N3 in visible region
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with increasing the concentration of the ZTO have been presented. The absorbance spectra of

ZTO in absence of the dyes are shown as a black curve. The gradual enhancement of MLCT1
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in Fig. 7(a) and (c) for both N719 and N3 having sufficient overlap with the emission region
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of donor ZTO indicates none other than the successful energy transfer from the emissive ZTO
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to the dye molecules exclusively in the early UVA region. It is worth mentioning the increase

in the absorption intensity of MLCT1 was of 31% for N719 with respect to the increase in the
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concentration of the donor ZTO whereas it was only of 24% for N3 and further corroborates
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the S-V fluorescence quenching phenomenon in a complementary way. Interestingly no

significant changes in MLCT2 of the dyes in Fig. 7(b) and (d) further rule out the possibility

of any kind of energy transfer in the visible region. The phenomena of energy transfer from

ZTO towards the sensitizers N719 and N3 dye have been further established by measuring

the fluorescence quantum yield (QY) of the ZTO solution in ethanol in the absence and

presence of the sensitizers N719 and N3. The quantum yield (QY) of ZTO fluorescence has

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been defined as the ratio of the number of the fluorescence quanta to the number of absorbed

quanta (Ifluorescence/Iabsorbed). At the outset, the solution of ZTO in ethanol in absence of the

acceptor sensitizers exhibited the QY of ~11%. Interestingly, a loss in QY (51%) was

observed with an overall QY of ~5% in presence of N719 whereas only a 38% decrease was

observed in presence of N3 exhibiting an overall QY of ~7%. This loss in QY elucidates the

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quenching of fluorescence due to energy transfer from the donor ZTO to the acceptor

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sensitizers which is due to the decrease in fluorescence lifetime of the donor in presence of

the acceptor. The greater loss in fluorescence quantum yield further supports the superiority

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in energy transfer in donor-acceptor pair of ZTO-N719 in comparison to ZTO-N3.

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However the synthesized ZTO having aforementioned interesting optical properties has been
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explored as a photoanode material during fabrication of the DSSCs device. The same is not

preferred as an effective sensitizer like other well known semiconducting oxides for example
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TiO2, ZnO etc. used for the identical purpose owing to the weaker molar excitation

coefficient, scarcity of redox state exchange or alternation during sunlight absorption, lack of
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extensive functional anchoring groups and most importantly due to the relatively narrow and
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fixed band gap [39].

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5. Photovoltaic performance of ZTO nanoparticles

Utilising the synthesized ZTO nanoparticles as photoanode, we fabricated DSSCs and the
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performance has been monitored with two different sensitizers, N3 and N719. In Fig. 8, the
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photocurrent density-voltage (J-V) characteristics of the selected fabricated cells with ZTO

with the sensitizers N3 and N719 are presented. All the photovoltaic properties have been

summarised in Table 1. The tested cells attained conversion efficiency of 1.62% and 1.90%

with N3 photosensitizer after sensitization for 8 hours and 12 hours, respectively, whereas an

enhanced efficiency of 1.88% and 2.56% was observed for N719 dye molecules under the

analogous dye loading conditions. Irrespective of the sensitizer, both the cells exhibited a

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high VOC of 0.76V, for the dye loading time of 12 hours. This appears to be highest Voc

among all the reported devices based on hydrothermally synthesized ZTO NPs. On the other

hand, the Fill Factor (FF) was higher for a relatively lower dye loading time of 8 hours. All

the above results encourage us to confirm that under identical conditions, N719 is a better

sensitizer than N3 for ZTO based DSSCs. In spite of that the eventual improvement in current

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followed by the conversion efficiency to a notable amount once more support in favour of the

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resonance energy transfer as the decisive factor for this kind of device performance where

there was not much variation in dye loading behaviour observed upon increasing the dipping

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time from 8 hours to 12 hours. In order to monitor the effect of concentration of the dye

molecules on the device, the concentration of dye has been varied. An improvement was observed

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after increasing the concentration of the dye molecules to double the previously measured
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concentration from 0.2 to 1.0 mM as shown in Fig. S3 (ESI). But, not much improvement was
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observed even after making the concentration double to the initial concentration. Rather the

efficiency got decreased with increase in the concentration of the dye molecules. This may be due
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to the unfavourable adsorption geometry of the dyes at higher concentration [40] unfavourable
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aggregation of the dye at higher concentration [41]. The typical trend of the performance of the

devices fabricated with ZTO NPs as a function of the concentration of N719 has been shown in
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Fig. S3 (ESI). The corresponding photovoltaic parameters recorded with different N719 dye
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concentration is tabulated in Table. T3 (ESI).

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Though the ZTO-N719 device exhibited a higher VOC, the observed performance is far below than

expected .Therefore it may be important to try with sensitizers having higher LUMO positions for

this particular ternary oxide used as photoanode where it will be possible to obtain higher

photovoltage. It is expected that different techniques of film preparation and device fabrication

with other electrolytes may improve the performance of ZTO based devices and the work is

underway.

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The photovoltaic parameters of the present study are compared with the previously reported

hydrothermally synthesized ZTO NPs of different size and are summarised in Table 2. Table

2 indicates that the conversion efficiency of DSSC is not directly governed by the size of

hydrothermally synthesized ZTO NPs rather it is varied throughout a wide range from as low

as 0.9% to as high as 4.7%. In addition, significant improvement in performance has not been

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achieved even after lowering the active area, increasing the dye loading time and modifying

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the photoanode by TiCl4 treatment [41-44]. As far as the present study is concerned several

other parameters, for example, the preparation of more stable paste of the ZTO following a

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modified route, implementation of different techniques to fabricate film preparation, exploration

of other electrolytes are underway in order to utilize the ZTO more effectively to improve its

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performance. The time dependent dye loading phenomenon of the ZTO NPs as exhibited in
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Fig. 4 (a)-(d) in the manuscript clearly indicates the better loading ability of N3 dye onto the
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photoanode surface than N79 dye. Albeit improved performance has been observed from the

ZTO-N719 based devices, various data available confirm that higher dye loading is not the
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only reason to achieve better performance. However, at this point it is difficult to ascertain
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the role of energy transfer in the performance of the studied devices.The mechanism of the

resonance energy transfer of ZTO nanoparticles and the sensitizers N719 and N3 showing the
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electronic transitions in the conventional DSSCs have been illustrated in Fig. 9. In

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conventional DSSC the role of harvesting sunlight mainly relies upon the dye molecules
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(Step 1). Consequently there occurs an electronic transition from the ground state (highest

occupied molecular orbital, HOMO) to the excited state (lowest unoccupied molecular

orbital, LUMO) of the sensitizer dyes (Step 2). The sensitized dye further injects electron to

the conduction band of the semiconductor photoanode (Step 3). The injected electron flows

through the semiconducting oxide film until it reaches the attached conducting substrate

contact where it is extricated to the external electrical circuit (Step 4). The reductant

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electrolyte reduces the oxidized dye molecules to its original state and simultaneously gets

reduced at the counter-electrode making the electrical circuit complete (Step 5 and 6). The

studied devices are expected to follow the above mentioned steps if it behaves like a

conventional cell. However, since the synthesized ZTO nanoparticles are able to absorb high

energy photon in the terminal UVA region depicted as UVAT in Fig. 9 (Step 7 and 8), this

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may further help in improving the performance further. Apart from the conventional

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functions as a photoanode, the optically active ZTO nanoparticles may be able to transfer the

energy (Step 9) through resonance energy transfer behaving as a ZTO-N3/N719 donor-

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acceptor pair. This eventually could provide a simultaneous pathway for sensitization activity

(Step 10).

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In our previous work on ZTO plates and ZTO particles which were not fluorescent, we
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observed much inferior efficiency compared to fluorescent ZTO nanoparticles reported here
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[22, 23, 34]. The fluorescent ZTO nanoparticles though exhibited enhanced photovoltaic

performance compared to ZTO plates and particles synthesized by us, but are still much
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lower than many of the reported results as demonstrated above with two different dye
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molecules.

6. Conclusions
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In conclusion, the ZTO NPs, with an average particle size of ~7 nm synthesized by a

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hydrothermal method exhibits a band to band emission in the mid UVA region. The emissive
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ZTO exhibited significant optical interactions with the predominantly visible photosensitizers

N719 and N3 dye molecules. An efficient transfer of the high energy photon from the ZTO

NPs to preferentially N719 have been established by comparing the extent of quenching of

the emission of the ZTO nanoparticles with the acceptors N719 and N3 and also by

determining the fluorescence quantum yield of Zn2SnO4 in presence and absence of the dye

molecules. The lower amount of residual dye and relatively closer hydrophilic nature of the ZTO

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NPs surface during time dependent adsorption study of the sensitizers indicates a better loading of

N3 by the hydrothermally synthesized ZTO NPs. As a consequence an enhanced conversion

efficiency of 2.56% was observed for the fabricated devices of ZTO -N719 than ZTO-N3

(1.90%). This establishes the studied ZTO as an important photoanode in harvesting of

relatively high energy photon in the terminal UVA region without using any additional

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sensitizers in a conventional DSSC. The resulted efficiencies may further be enhanced by

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using more stable paste of the ZTO and implementing different coating techniques for film

fabrication and exploring suitable electrolytes for the device.

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Acknowledgements

PSD acknowledges the Ministry of New and Renewable Energy (MNRE) for financial

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support under the CSIR-TAPSUN program. AR gratefully acknowledges the DST-INSPIRE
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program for the senior research fellowship to carry out his PhD.
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Figures

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Fig. 1. (a) The XRD pattern of the prepared Zn2SnO4 particles calcined at 500 and 900°C, (b)

TEM image of prepared Zn2SnO4, size distribution histogram (inset), (c) HRTEM image of

the sample, FFT of the corresponding HRTEM (inset) and (d) SAED pattern of the sample.

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Fig. 2. (a) FTIR spectra of the studied Zn2SnO4 nanoparticles (i.e., black curve indicates

annealed at 500oC and red curve indicates the same annealed at 900oC), (b) Raman spectra of

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the hydrothermally synthesized Zn2SnO4 nanoparticles, (c) separately measured UV-Vis

absorption spectra (black curve) and diffuse reflectance spectra (blue curve) of the same

synthesized Zn2SnO4 nanoparticles. Inset shows the corresponding Tauc’s plot and (d) room

temperature emission spectrum of the hydrothermally synthesized Zn2SnO4 nanoparticles

dispersed in ethanol excited at 320 nm. Inset: the excitation wavelength dependent emission

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spectra of the sample.

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Fig. 3. (a) XPS spectra of spin-orbit split peaks of Sn 3d, (b) Sn 4d, (c) spin-orbit split peaks

of Zn 2p and (d) spectral decomposition of the O 1s spectra results in two different types of

oxygen environment in the Zn2SnO4 nanoparticles, represented as O1 and O2.

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Fig. 4 (a)-(b) UV-vis absorption spectra of the residual N719 dye solution after loading for
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different times for N719 and N3 respectively (Inset: corresponding chemicals structure). (c)-

(d) plot of dye adsorption and contact angle measurement against the dye loading time for
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N719 and N3, respectively.

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Fig. 5. I-V characteristics of Zn2SnO4 before and after dye loading measured under the

illumination of UV and visible light separately. Black circles indicate the respective plots
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under two different light irradiation

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Fig. 6. (a) The room temperature emission spectra of Zn2SnO4 nanoparticles and absorption
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spectra of N719 (purple curve) and N3 (red curve). Normalisation of the plots has been done
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with respect to intensity 1. The spectral overlap areas have been shown as the shaded zones,

(b) and (c) the quenching of fluorescence of the Zn2SnO4 nanoparticles with increase in
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concentration of (1, 2, 3, 4, 5)× 10-7 M N719 and N3, (d) Stern-Volmer plot of the
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fluorescence quenching of the Zn2SnO4 nanoparticles as a function of the concentration of the

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sensitizers N719 and N3.

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Fig. 7. (a) and (c) MLCT1 of N719 and N3 with increasing the concentration of synthesized
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Zn2SnO4 nanoparticles from 0.1× 10-5 M depicted as (l) to 0.25× 10-5 M depicted as (h), (b)

and (d) MLCT2 of the same. The black curve in each plot represents absorbance spectrum of
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ZTO in absence of any dye sensitizers.

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Fig. 8. J-V characteristics of fabricated DSSCs with the synthesized Zn2SnO4 nanoparticles
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using N719 and N3 as photosensitizers

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Fig. 9. Schematic representation of the energy transfer dynamics within the photoanode
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material Zn2SnO4 and the sensitizers N719 and N3. The two systems have been represented

together.
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Tables

Table I. Photovoltaic properties of the Zn2SnO4 using the sensitizers N3 and N719 at two

different dipping times

Dye Used Dipping Time (h) Voc (V)±0.01 Jsc (mA/cm2)±0.02 FF (%)±0.05 ɳ (%)±0.01

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N3 8 0.71 3.08 72.54 1.62

N3 12 0.76 4.10 60.45 1.90

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N719 8 0.70 3.58 73.94 1.88

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N719 12 0.76 4.89 68.26 2.56

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Table II. Performance of hydrothermally synthesized different size of ZTO nanoparticles in DSSC
testing
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Size Dye Dye loading Active VOC FF Efficiency Modification/ References

(nm) concentration time area (V) (%) Properties of
(mM) (h) (cm2) Photoanode
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27 - 6h 0.32 0.68 0.68 1.0 Mechanical 4

pressed
20 0.17 24h 0.20 0.63 0.65 3.7 - 18
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20 0.3 - 0.25 0.71 0.61 2.3 - 41

60-70 - - 0.08 0.67 0.67 0.9 - 42
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8 - - - 0.68 0.75 4.7 - 43

16 0.5 20h 0.16 0.74 0.76 3.4 TiCl4 44
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treatment
7 0.5 12h 0.25 0.76 0.68 2.5 Emissive Current Work

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Hydrothermally synthesized fluorescent Zn2SnO4 nanoparticles for dye sensitized solar

cells

Partha Pratim Das†§, Anurag Roy†, Shruti Agarkar Ϯ and Parukuttyamma Sujatha Devi† *

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Highlights

1. Hydrothermally synthesised Zn2SnO4 nanoparticles exhibit extraordinary emission spectrum

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in the mid UVA region

2. Fluorescence quenching and quantum yield measurements support an effective resonance

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transfer between Zn2SnO4 and dye sensitizers.

3. N719 dye sensitized Zn2SnO4 films exhibited 34% higher efficiency than N3 dye sensitized

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film with a higher Voc of 0.76 V. AN
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