Optical Materials 121 (2021) 111557

Contents lists available at ScienceDirect

Optical Materials
journal homepage: www.elsevier.com/locate/optmat

Research Article

Optically photoactive Cu–In–S@ZnS core-shell quantum dots/biopolymer

sensitized TiO2 nanostructures for sunlight energy harvesting
Josué C. Amaral-Júnior , Alexandra A.P. Mansur , Isadora C. Carvalho , Herman S. Mansur *
Center of Nanoscience, Nanotechnology, And Innovation - CeNano2I, Department of Metallurgical and Materials Engineering, Federal University of Minas Gerais -UFMG,
Av. Antônio Carlos, 6627 – Escola de Engenharia, 31.270-901, Belo Horizonte/MG, Brazil

A R T I C L E I N F O A B S T R A C T

Keywords: Colloidal semiconductor quantum dots (QDs) have been intensively investigated because of their remarkable
Optical nanomaterials tunable optical and electrical properties for potential clean energy production through solar photoconversion
Quantum dots devices. Herein, we present for the first time the design and development of a hybrid nanostructure for appli­
Cu–in–S/ZnS
cations in sunlight energy photoconversion, relying on a “safe and sustainable by design (SSD)” strategy, as fol­
Green nanomaterials
lows: a) “Cadmium-free” (non-Cd-containing) inorganic semiconductor quantum dots (QDs), as optically active
Solar photoconversion
Clean energy nanomaterials composed of quaternary Cu–In–S/ZnS systems (ZCIS); b) carboxylic-functionalized cellulose de­
rivative (CMC) as biopolymer ligand and macromolecular stabilizing agent; c) A green chemistry approach based
on an aqueous synthesis at mild conditions (e.g., pH, temperature, “organic-free”, nontoxic precursors) for
creating water-soluble supramolecular colloidal core-shell nanostructures (i.e., ZCIS@CMC, core: ZCIS; shell:
CMC); d) As a proof-of-concept, the fabrication of a photoelectrochemical cell (PEC-cell) based on a solid-liquid
heterojunction using the photoanode composed of TiO2 sensitized by ZCIS@CMC nanohybrids. Regarding optical
properties, the results demonstrated that the ZCIS@CMC nanohybrids presented absorption/emission charac­
teristics with maxima responses within the visible range of the light spectrum, which is prospectively appropriate
for sunlight photoconversion applications. The solid-liquid junction photoelectrochemical cells (PEC-cell)
fabricated using TiO2 films deposited onto ITO glass slides sensitized by ZCIS QDs evidenced photoactivity under
visible light illumination using “dark” (“OFF”) and “light” (“ON”) cycles. Moreover, the PEC-cells confirmed the
significant enhancement of photoinduced current density (over 150%) upon illumination when the relative
sensitization density associated with the ZCIS QDs/TiO2 ratio was increased, and ethanol was used as the co-
solvent. The results were credited to better contact between ZCIS QDs and TiO2 nanoparticles, tailoring a
more favorable energy level alignment at the heterojunction interfaces, promoting the formation of a cascade of
conduction band edges. Thus, these quantum dot-sensitized nanostructures developed through a sustainable and
biocompatible approach produced strictly via green chemistry process can be anticipated as a sustainable
alternative to the existing heavy metal-based sunlight photoactive optical nanomaterials after further optimi­
zation of conversion efficiency parameters.

1. Introduction replacing fossil fuels for generating environmentally benign energy

Energy production relying on the combustion of limited fossil fuels is
considered highly hazardous to the environment through air pollution
and global warming, which poses serious health threats to all kinds of
life. Thus, there has been a drastic increase in the global demand for
clean energy produced from renewable sources through sustainable
strategies, which is one of the greatest challenges faced by mankind
[1–4]. Solar energy can play a critical role as a viable source for
where sunlight comprises several advantages, including the most
abundant, globally available, renewable, clean, and inexhaustible
source of energy [2–4]. The available supply of solar energy is about 15,
000-fold greater than the combined energy derived every year from
nuclear and fossil fuels for consumption [3].
In this view, nanotechnology has the potential to drastically revo­
lutionize this scenario of energy alternatives by offering innovative and
disruptive technologies that can be applied to harness solar energy and

* Corresponding author. Federal University of Minas Gerais, Av. Antônio Carlos, 6627 – Escola de Engenharia, Bloco 2 – Sala 2233, 31.270-901, Belo Horizonte/
MG, Brazil.
E-mail addresses: hmansur@demet.ufmg.br, herman.mansur2016@gmail.com (H.S. Mansur).

https://doi.org/10.1016/j.optmat.2021.111557
Received 6 July 2021; Received in revised form 24 August 2021; Accepted 3 September 2021
Available online 8 September 2021
0925-3467/© 2021 Elsevier B.V. All rights reserved.
J.C. Amaral-Júnior et al.
convert it to other energy forms (e.g., photoelectrochemical, photo­
concentrators, and photocatalysis) to be utilized by society [3,5–7].
Although the search for greener processes for producing nanostructures
has gained momentum in more recent years owing to crescent health
and environmental concerns, appropriate attention must be paid to
conduct a sustainable strategy for designing, producing, and using
engineered nanomaterials (EMNs) and EMN-enabled products, referred
to as “safe and sustainable by design (SSD)”. The comprehensive concept
of “SSD” encompasses all stages of ‘the process, covering the design,
selection of materials, synthesis and production, functional perfor­
mance, life-cycle, hazards, and toxicity as well as social and economic
aspects [8–11]. Unfortunately, it has not always been followed, where,
by optimizing performance and costs, human health and environment
have been frequently overlooked or neglected in the development pro­
cess of EMNs [8–10].
In this context, inorganic semiconductor nanocrystals, widely used
as optoelectronic materials, have emerged as attractive photoactive
nanomaterials, which can harness the incoming solar light, a clean en­
ergy source from electromagnetic radiation, and convert into electrical
and chemical forms [1–4,6,12–14]. In particular, a new class of colloidal
inorganic semiconductor nanomaterials, termed quantum dots (QDs),
has garnered crescent interest because they possess the equivalent op­
tical and electronic properties of bulk semiconductor counterparts, but
also, they present other remarkable characteristics created by the
“quantum confinement effects” owing to their extremely small dimension
(e.g., <10 nm) [15]. QDs exhibit strong quantization effects as a result of
the exponential increase of the surface atoms compared to the volume of
the nanoparticles, leading to a unique set of optoelectronic properties.
Therefore, besides the chemical composition, their energy band struc­
tures are considerably size-dependent, which can be tuned for solar
energy photoconversion applications [12–14]. Hence, the research of
colloidal semiconductor QDs and other types of nanomaterials (e.g., can
contribute largely to the field of sustainable and green clean energy by
offering advanced functional nanomaterials for sunlight energy con­
version [12,13].
However, colloidal QDs have been synthesized with several chemical
compositions, but predominantly with binary semiconductors composed
of “heavy metal” chalcogenides (e.g., II-VI, CdX, X = S, Se, Te; and IV-VI,
PbX, X = S, Se, Te) [1]. Moreover, focusing mostly on boosting opto­
electronic features, the synthesis processes have been executed through
organometallic solvents and highly toxic precursors (i.e., Cd2+, Hg+,
Pb2+), usually at high temperatures, which are not sustainable.
Although these QDs often possess strong light absorption coupled with
size-tunable emissions, high photoluminescence quantum yield (QY),
these processes usually produce hydrophobic nanoparticles. Thus, they
are virtually insoluble in aqueous media hampering their potential use
in several fields of biomedical applications and environmental tech­
nologies [1,15]. These drawbacks have posed serious health and envi­
ronmental concerns contradictory to the sustainable concept connected
with clean and renewable solar energy research and applications.
Consequently, greener synthesis routes have been developed for pro­
ducing QDs based on sustainable processes using “heavy-metal free” (e.
g., “Cd– Pb-free”) semiconductor nanoalloys (e.g., ZnX and Bi2X3, X = S,
Se), which can be stabilized by water-soluble ligands, rendering
eco-friendly and biocompatible optically functional nanomaterials [16,
17]. However, these are limited alternatives of chemical compositions (i.
e., bandgap energy) to permit their suitable applications as sunlight
photoconverters. So, more recently, ternary I–III–VI chalcogenide
nanocrystals (e.g., M1M2X, M1 = Ag, Cu; M2 = In; X = S, Se) have
appeared as one of the most broadly acknowledged greener nano­
materials with tunable emissions spanning from visible to NIR spectral
windows [18,19]. They hold great potential for clean and renewable
energy applications [13]. To this end, through aqueous processes, it is
feasible to design and synthesize ternary QD nanoalloys comprising the
chemical composition, controllable size, and morphology to accurately
tune their optical properties for energy harvesting applications.
2
Optical Materials 121 (2021) 111557
Nonetheless, water-based processes may adversely affect the optical
properties of QDs due to the higher density of surface and crystalline
defects, which facilitate the charge recombination via non-radiative
pathways reducing the efficiency [16–19]. Fortunately, it can be
improved by several alternatives, including the semiconductor chemical
composition (i.e., binary, ternary, multinary alloys), post-synthesis
thermal annealing, and growth of a wide bandgap semiconductor
layer on the original QD for passivating their surface defects. Further­
more, the appropriate selection of water-soluble functional macromo­
lecular ligands such as polymers has been intensively investigated
because they play a central role during the nucleation, growth, and
stabilization of the colloidal QDs [16–19]. Therefore, in recent years,
polysaccharides and derivatives (semi-processed) obtained from
renewable and sustainable sources, such as carboxymethyl cellulose
(CMC), have gained increasing attention from researchers for producing
water-dispersible QDs, through green aqueous colloidal processes and
under mild synthesis conditions, mostly focusing on advanced biomed­
ical and environmental applications including solar cells [16,17,20,21].
Thus, the amalgamation of these unique characteristics makes
water-soluble colloidal QDs prospective candidates for sustainable
technological applications, including solar energy conversion [22].
Among different techniques for evaluating solar energy conversion of
nanomaterials and devices, the photoelectrochemical (PEC) method that
generates chemical or electrical energy based on nanomaterials (e.g.,
QDs, perovskite nanocrystals, etc.) photoactivity has become a very
practical and attractive solution [5–7,23,24]. To this end, quantum dot
sensitized solar cells (QDSSC) are considered the novel third-generation
of solar cells owing to their suitable optoelectronic characteristics for
photovoltaic response [23,24]. The sensitization process is achieved by
the decoration of semiconductor QDs onto one-dimensional (1D) metal
oxide nanostructures (e.g., TiO2 and ZnO films) for constructing photo­
active electrodes owing to the amalgamation of properties of these
wide-bandgap semiconductors. They comprise tunable bandgap, energy
band structure alignment, large absorption coefficient, multiple exciton
generation, as well as a simple and low-cost process [23,24]. Ideally, the
entire process should be sustainable, although the most reported
QD-based photoelectrodes include toxic cadmium and lead species,
which can limit their prospective commercial use, taking into account
environmental and health issues. Consequently, the development of
efficient and nontoxic QD-type photoabsorbers is highly needed for their
use as clean sunlight-harvesting nanomaterials for the absorption and
conversion of solar light in the visible region [1,3,25,26].
Unexpectedly, despite the intensive research conducted in recent
years based on I–III–VI QDs for several optoelectronic applications [1,
18,27–29], no report was found in the consulted literature incorporating
the whole concept of “SSD” at all stages of the process, through a sus­
tainable and green synthesis approach, for producing biocompatible
non-stoichiometric Cu–In–S@ZnS quantum dots using CMC biopolymer
as capping ligand, strictly based on aqueous colloidal chemistry.
Moreover, these nanohybrids were used for the assembly of PEC-cells
using a solid-liquid junction based on the photoanode composed of
TiO2 sensitized by ZCIS@CMC nanoconjugates, suitable for prospective
photoconversion of clean solar energy.
2. Materials and methods
All of the materials, procedures, and conventional characterization
techniques are detailed in Supplementary Information (SI).
2.1. Synthesis and characterization of QDs
ZCIS QDs were synthesized via an aqueous route using carboxy­
methylcellulose (CMC) as capping ligand and salts of metals (Zn, Cu, and
In) and sulfide precursors [30].
Colloidal quantum dots were characterized for evaluation of their
spectroscopic, morphological, and structural properties using
J.C. Amaral-Júnior et al.
ultraviolet–visible (UV–vis) and photoluminescence (PL) spectroscopy,
transmission electron microscopy (TEM), Fourier-transform infrared
spectroscopy, X-ray photoelectron spectroscopy (XPS), dynamic light
scattering (DLS), and zeta potential. The nanotoxicity in vitro was
assessed using 3-(4,5-dimethylthiazol-2yl)-2,5-diphenyltetrazolium
bromide (MTT) protocols and measurements of reactive oxygen species
(ROS).
2.2. Preparation and characterization of photoanode
The photoanode was based on indium tin oxide (ITO)/TiO2/ZCIS
heterostructures. TiO2 film was fabricated by screen printing of the
suspension deposited onto the ITO glass slide, followed by drying/sin­
tering steps. Then, the sensitization process was achieved by the deco­
ration of ZCIS@CMC onto the TiO2 layer. The heterostructures were
thermally treated at 350 ◦ C for 24 h to partially remove the CMC ligand.
Samples with different QD densities, 50, 100, and 200 μg cm− 2, were
prepared, referred to as ZCIS@CMC _50_350T, ZCIS@CMC_100_350T,
and ZCIS@CMC_200_350T, respectively. Also, an electrode was con­
structed using ethanol as a co-solvent for QD dispersion at the density of
100 μg cm− 2 (ZCIS@CMC/E_100_350T). The morphological and spec­
troscopic characteristics of the surface of ZCIS@CMC/E_100_350T were
evaluated using scanning electron microscopy (SEM) and atomic force
microscopy (AFM), as well as PL, FTIR, and XPS spectroscopy
techniques.
Fig. 1. Characterization of ZCIS QDs “as prepared”: (a) UV–vis (I) and PL (II) curves; (b) 3D excitation-emission plot; (c) Pathways of radiative decay; (d) TEM image
with the histogram of the size distribution (inset); and (e) Schematic representation of the core-shell structure of ZCIS core and CMC polymer indicating DH and ZP
values (not to scale).
3
Optical Materials 121 (2021) 111557
2.3. Photoelectrochemical solar cell test
The photoelectrochemical cell (PEC-cell) system was based on the
three-electrode setup with the ITO/TiO2/ZCIS acting as the working
electrode, and of Na2S (0.1 M) and Na2SO3 (0.1 M) as a dual-electrolyte
solution. A LED lamp was used as the “visible” light source, and the
current recording and the bias application were based on cyclic vol­
tammetry. (All details can be found in the Results and Discussion section
and Supplementary Information - SI).
3. Results and discussions
3.1. Characterization of colloidal quantum dots
ZCIS quantum dots were synthesized via the aqueous colloidal route
in a two-step procedure by deposition of a ZnS layer over non-
stoichiometric (Cu-deficient) Cu–In–S nanocrystals followed by
annealing at 100 ◦ C/1 h using CMC polymer as the stabilizing agent.
UV–visible spectrum (Fig. 1a(I)) of ZCIS suspension did not present a
clearly defined excitonic peak, with an absorbance onset at approxi­
mately 580 nm. These features are characteristic of Zn–Cu–In–S qua­
ternary systems, mostly associated with sub-bandgap optical transitions
involving point defects [19,30], that could allow the exploitation of
solar spectrum for the generation of electrochemical energy through
photoconversion. Based on UV–vis results, the Tauc curve was obtained
(Figs. S1–SI) and indicated that the bandgap (Eg) value was 2.50 eV
J.C. Amaral-Júnior et al.
(496 nm). This result is larger than the bulk counterparts with a stoi­
chiometric ratio of CuInS2 (Ebulk = ~1.5 eV) and In2S3 (Ebulk = 2.0–2.2
eV), and red-shifted compared to the ZnS (Ebulk = ~3.7 eV), as expected
for Zn–Cu–In–S alloys, which demonstrated the formation of ZCIS QDs
[30,31].
The emission properties of quantum dots are very important for
photoconversion application as it reveals the electronic structure and
recombination behavior of the nanocrystals. First, the PL spectrum
(Fig. 1a(II)) illustrated that ZCIS@CMC QDs have a broad emission
spanning from green to NIR (near-infrared) with a maximum intensity at
663 nm. The large Stokes shift estimated using Eg and PLmax, (164 nm or
630 meV) could minimize the self-reabsorption of its emission and
indicated a radiative emission associated with intragap energy levels.
For a more in-depth analysis, 3D excitation-emission contour curves,
quantum yield (QY), and lifetime decay curves were obtained. The 3D
plots (Fig. 1b) demonstrated a broad range of excitation wavelengths,
from UV to visible, with a reasonable spectral match with solar radiation
and also confirmed the emission window in the green-NIR. Considering
the solar photoelectrochemical conversion purposes, QY values are
important as they are intrinsically related to photocurrent density [32].
ZCIS@CMC showed a QY of 6.5%, which can be considered a high value
for QDs synthesized through an aqueous route and low/mild tempera­
tures that are required to fulfill the concept of “safe and sustainable by
design”. PL lifetimes influence the carrier radiative recombination and
the charge collection efficiency at the electrode. Higher lifetimes tend to
enhance the probability of charge collection, reducing recombination.
The relaxation profile of ZCIS@CMC followed a three-exponential
decay, indicating three different recombination pathways (τ1, τ2, and
τ3). The higher contribution (amplitude, A1, 87%) was observed for the
component with the longest lifetime (τ1 = 288 ns) that may be associ­
ated with donor-acceptor (D-A) transitions arising from point defects.
Due to Cu-deficient synthesis conditions, energy level related to copper
was also observed with A2 = 52% and τ2 = 52 ns, resulting in a smaller
effect in the average lifetime. The third component is a negligible
contribution assigned to excitonic recombination (A3 = 1% and τ3 = 3
ns). The average PL lifetime (τav) based on these three mechanisms was
256 ± 62 ns. It is important to focus that this value is greater than those
usually measured for QDs based on highly toxic elements (e.g., Cd-, Pb-)
[1], which is favorable for charge separation processes, such as in
PEC-cells. Fig. 1c summarizes the radiative recombination pathways
identified for ZCIS@CMC colloidal quantum dots.
The morphology and size of ZCIS QDs were accessed by TEM images
(Fig. 1d), which demonstrated the formation of fairly monodisperse
nanoparticles with a spherical-like shape. The histogram of the nano­
particle size distribution indicated an average value of 4.7 ± 0.8 nm
(Fig. 1d, inset). This size evaluated by TEM is predominantly related to
the inorganic semiconductor core (ZCIS) of the nanoconjugates as the
organic polymer shell has low electron contrast. Moreover, electron
energy-loss spectroscopy (EELS) analysis (Figs. S2–SI) confirmed the
presence of the chemical elements of ZCIS QDs (Zn, Cu, In, and S) in
addition to C and O from CMC.
The hydrodynamic diameter (DH) of the colloidal ZCIS QDs,
involving the sum of the contribution of the inorganic core with the CMC
polymer coating as well as its interactions with the surrounding aqueous
medium, resulted in DH = 29.9 ± 0.4 nm. The surface charge of ZCIS
nanocolloids determined by zeta potential (ZP) measurements was -
41.9 ± 11.0 mV. This ZP value (ZP < − 30 mV) indicated that the sta­
bilization of the nanocolloids was promoted by the anionic carboxylic
groups of CMC capping agent (R-COO-). The schematic representation of
DH, and ZP results is presented in Fig. 1e, revealing the supramolecular
structure of synthesized colloidal ZCIS.
FTIR spectra of CMC (Figs. S3a–SI) polymer indicated the main
groups present in the polysaccharide (carboxylates, carboxylics, alco­
hols, glycoside bonds, and methylene) [33]. When comparing the
spectra of ZCIS@CMC nanoconjugates (Figs. S3b–SI) with CMC polymer
separated changes in the intensities carboxylic (COOH, νC = O at 1730
4
Optical Materials 121 (2021) 111557
cm− 1 and νC-O at 1245 cm− 1) and carboxylate (COO− , νas at 1650 and
1590 cm− 1 and νs at 1420 and 1325 cm− 1) bands were detected. This
could be associated with the formation of the monodentate and biden­
tate metal-carboxylate complexes evaluated by the wavenumber dif­
ferences between the asymmetric and symmetric vibrations (Δν1 and
Δν2) [33]. Additionally, the coordination of surface metal ions with
hydroxyl groups of CMC promoted changes in the absorbance in the
region related to hydrogen bonds region (3700-3000 cm− 1) and C–OH
vibrations of alcohol groups (1200-1000 cm− 1).
High-resolution XPS spectra (Figs. S4–SI) obtained after removing
the CMC shell over QD surface by Ar+ ions (2 cycles, 3 s/each, beam
voltage 0.5 kV, and emission current 20 mA) showed all of the elements
of QDs with identified oxidation states (Zn2+, Cu+, In3+, and S2− ) that
are characteristic of Zn–Cu–In–S quaternary systems [30].
Bearing in mind the concept of “safe and sustainable by design”, the
non-toxicity of ZCIS QDs needs to be evaluated for prospective sus­
tainable applications. Thus, oxidative stress is a frequently reported
phenomenon related to the toxicity of nanoparticles. The imbalance in
the rate of formation of reactive oxygen species (ROS) leads to oxidative
stress and the consequent production of highly toxic species that can
cause harmful effects in biota [34]. To investigate the potential nano­
toxicity of ZCIS@CMC nanoconjugates, cell viability assays and evalu­
ation of reactive oxygen species generation were performed [35]. 3-(4,
5-dimethylthiazol-2yl)-2,5-diphenyltetrazolium bromide (MTT) mito­
chondrial activity assay are widely accepted to evaluate the toxicity of
nanomaterials in vitro [36]. The cell viability results of HEK 293T cells
after 24 h of incubation with CMC and ZCIS (Figs. S5a–SI) demonstrated
that, within the statistical variation, no difference was verified in the
response of the cells with polymer ligand (95%) and quantum dots
(97%) compared to the negative control condition (~100%). Regarding
oxidative stress, the intracellular level of ROS was evaluated using the
2′ ,7′ -dichlorodihydrofluorescein diacetate (DCF-DA) that, upon reaction
with some reactive oxygen species, is converted to the highly fluorescent
2′ ,7′ -dichlorofluorescein (DCF). No significant fluorescence was detec­
ted for cells treated with CMC and QDs (Figs. S5b–SI), in comparison to a
positive control (tert-butyl hydrogen peroxide, TBHP), demonstrating a
low level of accumulation of hydrogen peroxide (H2O2), hydroxyl (HO⋅),
and peroxyl (ROO⋅) toxic species in the cells [37]. These findings vali­
dated the hypothesis of non-toxicity of quaternary ZCIS QDs capped by a
renewable cellulose polymer derivative (CMC).
3.2. Characterization of PEC photoanode
The morphology of the surface of ITO/TiO2/ZCIS heterostructures
before (Fig. 2a and Figs. S6a–SI) and after (Fig. 2c and Figs. S6b–SI)
thermal treatment that followed ZCIS QDs deposition (ZCIS@CMC/
E_100_350T) was observed using scanning electron microscopy (SEM).
High magnification (20,000 X) images (Fig. 2a and c) revealed the TiO2
layer with a relatively uniform scattered distribution of pore that indi­
cated a high surface area for QD sensitization. Moreover, before the
thermal treatment at 350 ◦ C, the presence of smoother and continuous
regions at the surface was associated with ZCIS QDs embedded in CMC
polymer film, which was partially removed upon temperature thermal
treatment for promoting a better contact among QDs and TiO2
nanoparticles.
3D excitation-emission curves obtained from the surface of ITO/
TiO2/ZCIS electrode indicated that, before thermal treatment (Fig. 2d),
it was observed the radiative recombination of the excited electron with
similar wavelength ranges and PLmax of colloidal QDs (Fig. 1b). After the
thermal treatment (350 ◦ C), no fluorescence emission was detected at
the same experimental conditions (Fig. 2e). This result evidenced that
the presence of CMC restricted the injection of the excited e− from ZCIS
QDs into the TiO2 layer causing the recombination of excitonic charges.
On the contrary, for the thermally treated heterostructure, the lack of
fluorescent behavior was ascribed to the effective charge separation
process and carriers transport in the bandgap energy cascade, although
J.C. Amaral-Júnior et al. Optical Materials 121 (2021) 111557

Fig. 2. SEM images of photoanode (ZCIS@CMC/E_100_350T): (a) before and (c) after thermal treatment (inset: digital images). (b) TG (I) and DSC (II) curves for
ZCIS@CMC. (d) 3D excitation-emission profiles were obtained from the surface of the photoanode without thermal treatment and (e) after heating at 350 ◦ C. (f) FTIR
and (g) XPS analysis at the photoanode surface (I) before and (II) after thermal treatment.

some emission decay through non-radiative pathways may also have
occurred.
For a more in-depth characterization of the sensitized anode, thermal
analysis, FTIR, and XPS assays were performed. Thermogravimetric
(TG) and Differential Scanning Calorimetry (DSC) profiles (Fig. 2b) of a
ZCIS@CMC film heated up to 400 ◦ C indicated two major steps of mass
losses. The first is an endothermic event that is assigned to the evolution
of the water/alcohol, including the removal of free (<110 ◦ C) and tightly
bound solvents (110–180 ◦ C). The second stage (230–400 ◦ C) is the
exothermic thermal degradation of the polymer through complex
mechanisms and involving several reactions [38]. As the overall bal­
ance, both steps lead to a mass loss of approximately 40% at 350 ◦ C

5
J.C. Amaral-Júnior et al.
associated with organic removal.
The analysis of photoanode surface before (a) and after (b) heating at
350 ◦ C using FTIR (Fig. 2f) indicated the reduction/disappearance of the
peaks associated with the alcohol (1150–1000 cm− 1 region) and
carboxylate groups (1650, 1590, 1420, and 1325 cm− 1). Also, the
broadband at 1720-1500 cm− 1 overlapped the contributions of aromatic
C–– C (1650-1500 cm− 1) and remaining/formed C– – O (1720-1590
cm− 1) vibrations. XPS analysis (Fig. 2g) confirmed the FTIR results with
the presence of bands corresponding to C– – O and of C– – C aromatic
structures (π-π*). These findings are in agreement with the published
literature [38,39], which reports that several gases and water vapor are
generated by the pyrolysis of cellulose due to the breaking of bonds
related to functional and weak groups resulting mostly in the formation
of cyclic and/or aromatic carbon structures in an extension dependent
on the temperature rise. These findings support the hypothesis that
suppression of luminescence in thermal treated ITO/TiO2/ZCIS elec­
trode was mainly promoted by charge transfer due to the reduction of
Fig. 3. (a) EDX elemental image mapping; (b) High-resolution XPS analysis ((I) Ti, (II) Zn, (III), Cu, (IV) In, and (V) S); and (c) AFM 3D image obtained at the
electrode surface.
6
Optical Materials 121 (2021) 111557
the optical pathlength between TiO2 and ZCIS as a result of the degra­
dation of CMC with simultaneous formation of unsaturated structures
with more conductive behavior.
Regarding chemical composition and distribution of elements in the
photoanode after the thermal treatment, EDX elemental image mapping
directly over the surface showed that Ti, Zn, Cu, In, and S were uni­
formly distributed on the electrode (Fig. 3a), showing that ZCIS QDs
were successfully deposited on the TiO2 film. In addition, XPS was also
performed (Fig. 3b) to determine the surface chemical composition of
the fabricated ITO-TIO2-ZCIS_TT350 electrode. The value of the binding
energy of Ti 2p1/2 at 464.3 eV and Ti 2p3/2 at 458.6 eV was compatible
with Ti2+. Each group of spin-orbit components was separated by a
binding energy interval of approximately 5.7 ± 0.3 eV, which is char­
acteristic of TiO2. The peaks at approximately 1045.2 and 1022.1 eV (Δ
= 23.1 ± 0.3 eV) corresponded to Zn 2p1/2 and Zn 2p3/2, respectively,
which confirmed that Zn element existed mainly as Zn2+ on the sample
surface. The XPS spectrum of Cu 2p at 952.6 eV (Cu 2p1/2) and 932.5 eV
J.C. Amaral-Júnior et al.
(Cu 2p3/2), combined with the absence of a strong satellite band at
940–945 eV, confirmed the presence of Cu photocathode in the oxida­
tion state of Cu+. The high-resolution spectrum of In 3d region showed
the peaks of In 3d3/2 at 452.3 eV and In 3d5/2 at 444.8 eV (Δ = 7.5 ± 0.3
eV), which corresponded to In3+. The binding energies of S 2p1/2 and S
2p3/2 were at 162.5 and 161.4 eV (Δ = 1.1 ± 0.3 eV), respectively which
indicated sulfur-metal bonds [30].
These results showed the presence of the TiO2 layer sensitized by
QDs at the surface of the electrode. In addition, it indicated that the
thermal treatment did not affect the surface oxidation states of the
nanoparticles, which remained the same as detected for ZCIS@CMC
suspensions (Figs. S4–SI). To conclude, AFM imaging showed two major
nanosize structures (Fig. 3c, arrows), where the smaller was related to
ZCIS QDs and the other, with higher dimensions, associated with sin­
tered TiO2 nanoparticles. The TiO2 layer was coated with well-
distributed ZCIS, which favors electrons transfer from the QD to TiO2.
Topographical AFM image (Figs. S7–SI) also revealed that pores in the
TiO2 layer were observed, which may allow for the electrolyte to
penetrate into the photoanode structure, reaching QDs that are not at
the outermost surface.
3.3. TiO2/ZCIS QD sensitized PEC-Cell
The photoelectrochemical cell (PEC-cell) system has been widely
accepted as a reliable and relatively rapid technique for evaluating the
potential photoconversion activity of QD semiconductors relying upon
the solid-liquid heterojunction behavior [40,41]. PEC systems are based
on the three-electrode setup with the QD semiconductor photoanode (i.
e., TiO2/ZCIS) as the working electrode, the counter electrode (i.e., brass
plate), and the reference electrode (i.e., saturated Ag/AgCl). The
Ag/AgCl electrode was chosen because it is a very stable reference
electrode, simpler in construction than the SCE (saturated calomel
electrode, Hg2Cl2), and it contains no highly toxic mercury. The redox
electrolyte couple should possess hole (h+) scavenging properties
(S2− /SO32− ), which favors the charge separation (exciton, e− /h+)
generated upon light irradiation in the semiconductor nanocrystals at
the colloidal solid-liquid interface in aqueous media [40,41]. The
schematic representation of this entire photoelectrochemical process
based on ZCIS/TiO2 designed and constructed in this work is depicted in
Fig. 4a. Essentially, QDs are excited by absorbing incoming photons,
generating quasi-particles excitons (i.e., coupled electron/hole pairs,
e− /h+). Next, they can recombine, or they can undergo a charge sepa­
ration process, where the electrons are then injected into the TiO2
conduction band, and the holes migrate towards the
semiconductor-liquid interface where they will be captured by
hole-scavenging species in solution. Subsequently, the electrons go
7
Optical Materials 121 (2021) 111557
through an external circuit on arriving at the counter electrode. Finally,
semiconductor QDs can be regenerated by the redox couple of an elec­
trolyte solution [42]. According to the literature of similar PEC systems
based on QDs and sensitized-TiO2 films [40,41,43,44], the major
chemical reaction steps expected to occur are presented in Eqs. (1)–(5)
[40,41,43–46]. It should be emphasized that the electron (TiO2(e− )), Eq.
(5), originated from the electron-hole pair photoexcitation in Eq. (1),
must percolate through the nanostructured multi-component film before
reaching the ITO conductive layer. Thus, the efficiency of this stage will
affect the electron current flow.
Excitation: ​ ZCIS + hv →ZCIS ( (1)
(
Recombination: ​ ZCIS (2)
Charge separation by injection from ZCIS QD to TiO2:
ZCIS ( (3)
Hole scavenging by electrolyte solution with S 2−
:
(
ZCIS (h+ ) + TiO2 (4)
(
Reduction ​ reaction:ZCIS + TiO2 (5)
3.3.1. PEC-cell performance - Effect of QD sensitization density
To perform the required characterization of QDSCs, we probed the
influence of the relative ZCIS-QD concentration used in the TiO2 films
for the preparation of ZCIS-QD/TiO2 nanocomposite (termed as “sensi­
tization density”, SS), where other parameters were maintained constant
(i.e., deposition method, film thickness, thermal processing profile, etc.).
Fig. 5a shows the typical photocurrent–voltage (J–V) curves of PEC cells
under the irradiation based on the sensitization density ratios of ZCIS-
QD/TiO2 (0:“non-sensitized” – Pure TiO2; 50, 100, and 200 μg cm− 2) of
the nanocomposite structures.
The photovoltaic parameters Voc, Jsc, fill factor (FF), and the per­
centage power conversion efficiency (PCE or η) of each tested cell that
was obtained from the J–V curves are summarized in Table 1. As a
general tendency, it was observed that, when the relative amount of
sensitizer ZCIS-QDs in the TiO2 nanostructure was increased from 50 to
200 (μg cm− 2), the Voc, Jsc (Fig. 5b), and PCE values were systematically
increased, whereas the FF values retained practically constant. More
specifically, these parameters (Figs. S8–SI), except for FF, were signifi­
cantly affected by increasing the sensitization density of ZCIS-QD/TiO2
in the photoanode.
This behavior is suggested to be associated with the enhancement of
the charge transfer process promoted by the relative increase of the
interfacial contact between the two semiconductors, ZCIS QDs (medium
Fig. 4. (a) TiO2/ZCIS solar cell components
and operation. (b) Schematic representation
of the possible alignment of energy levels of
TiO2 and ZCIS QDs, resulting in a cascade of
conduction band edges in the order
Cu–In–S/ZnS > TiO2. Such an energy
cascade is expected to promote a stronger
driving force for the injection of photoex­
cited carriers from Cu–In–S/ZnS QD into
TiO2 that leads to more photoinduced elec­
trons from ZCIS QDs (conduction band, CBZ)
being injected into TiO2 (conduction band,
CBT).
J.C. Amaral-Júnior et al. Optical Materials 121 (2021) 111557

Fig. 5. (a) J-V curve. (b) Short-circuit current density (JSC). (c) Schematic drawing of the effect in the ZCIS QDs packing on the surface of the TiO2 layer by varying
the relative ZCIS/TiO2 sensitization density in the process (not to scale). (d) “Light-ON-OFF” cycle tests results of TiO2 photoanodes sensitized with different ZCIS QD
concentrations. (I) TiO2, (II) ZCIS@CMC_50_350T, (III) ZCIS@CMC_100_350T, and (IV) ZCIS@CMC_200_350T.

Table 1
Average Photovoltaic Performance and Standard Deviation Extracted from J–V measurement curves of QDSCs corresponding to different concentrations of ZCIS QDs in
the TiO2 films and co-solvent effect.
Photoanode VOC (mV) JSC (μA cm− 2) Fill Factor (FF) Efficiency (PCE, %) Δ Efficiency (%)

Control Pure TiO2 (non-sensitized) 715 ± 32 16.1 ± 2.3 0.52 ± 0.02 0.09 ± 0.01 –
Effect of ZCIS sensitization density ZCIS@CMC_50_350T 650 ± 50 20.07 ± 3.6 0.55 ± 0.01 0.09 ± 0.03 0
ZCIS@CMC_100_350T 762 ± 29 32.5 ± 0.5 0.50 ± 0.01 0.12 ± 0.01 +33
ZCIS@CMC_200_350T 767 ± 41 47.0 ± 4.5 0.52 ± 0.02 0.17 ± 0.02 +88
Effect of co-solvent ZCIS@CMC/E_100_350T 930 ± 61 125.6 ± 8.4 0.60 ± 0.01 0.70 ± 0.06 +670

bandgap) and TiO2 nanoparticles (wide bandgap), as schematically media [42,47].

illustrated in a Fig. 5c. Consequently, this morphological arrangement
would have favored the separation of charge carriers (h+/e− ) by the
bandgap alignment of the semiconductors cascade (Fig. 4b). Although
not directly observed, due to the resolution limitation to accurately
characterize this complex multi-component three-dimension nano­
structure of the photoanode, this study offers supporting evidence to
corroborate that this trend is feasible to have occurred based on the
results of XPS, EDX, AFM before and after the sensitization of TiO2 with
ZCIS QDs (data and details in Fig. S9 - supplementary information).
Moreover, a more in-depth investigation of the charge transfer mecha­
nism at the semiconductor interfaces is beyond the scope of this
research, which would certainly require the combination of additional
very sophisticated characterization techniques (e.g., EELS, HRTEM, and
elemental mapping by Auger electron spectroscopy).
Thus, that improved the photovoltaic performance of the cell by
allowing higher electron flow (i.e., Jsc) throughout the nanostructured-
based electrochemical device. As noted, the FF parameter was almost
unaffected by the QDs density, which was assigned to the fact that it is
typically related to the series and shunt resistances of the PEC solar cell,
indicating a relative constancy of the contacts at the solid-solid and
solid-liquid interfaces, as well as the stability of the dual-electrolyte
The additional rise in the sensitization density ZCIS-QD/TiO2 beyond
200 μg cm− 2 (e.g., 300 μg cm− 2, data not shown) has not provoked
further improvement of the P–V parameters. This was interpreted as the
system reaching a plateau value of the overall coverage and packing of
ZICS QDs incorporated in the TiO2 films, where a higher concentration
of ZICS QDs would have less effectiveness by promoting agglomeration
instead of increasing the contact with TiO2 nanoparticles. Consequently,
the sensitization density ZCIS-QD/TiO2 of 200 μg cm− 2 was considered
the optimized value for the PEC-Cell developed in this study. Similar to
Jsc, but with a less prominent effect, the increase of Voc was assigned to
the superior contact at the ZCIS-QD/TiO2 interfaces.
The higher loading density has led to an improvement in the charge
separation process upon irradiation, which declined the recombination
pathways through intermediate intraband electronic states (e.g., surface
states, intrinsic defects, etc.). Thus, it has favored the Voc towards the
theoretical approximation to the energy potential of bulk value (i.e., Eg
= VC – VB ~ -qVoc) [42,48].
Bearing in mind the prospective applications in solar cell photo­
conversion, the preliminary photovoltaic activity of the ZCIS/TiO2
electrode and their stability with time were evaluated. So, “light-ON-
OFF” cycle tests were performed, where a cycle consisted of 10 s of

8
J.C. Amaral-Júnior et al.
“dark” (“light-OFF”) followed by 10 s under illumination (“light-ON”).
The cycle was repeated three times with an applied voltage bias of +200
mV vs. reference electrode in order to stabilize the baseline and mini­
mize the impact of background, while the photocurrent density gener­
ated was recorded, and the results are presented in Fig. 5d. The results
proved the photoconversion activity of the systems under illumination
as well as the relative stability throughout the 3 cycles, with current
density fairly constant at “light-ON stages”. Moreover, a noticeable
enhancement of the photocurrent generated was observed of over 150%,
from nearly 20 μA cm− 2 to 50 μA cm− 2, by increasing the sensitization
density of ZCIS QDs onto TiO2 films from 50 to 200 μg cm− 2, respec­
tively. This trend was ascribed to the improvement of interfacial contact
of ZCIS QDs with TiO2 films increasing the overall surface coverage area.
This feature promoted increased electron flow throughout the nano­
structured assembly combined with a superior flow in the external
electrochemical circuit, in agreement with the literature in analogous
QD-based PEC-cells [49,50].
3.3.2. PEC-cell performance - Effect of ethanol co-solvent addition to
improving QD loading onto TiO2 surface
To further investigate the influence of QD loading in the TiO2 film on
the performance of the sensitized PEC-cell, ethanol was used as a co-
solvent (50% v/v) before the deposition process of the colloidal solu­
tion of ZCIS nanoconjugates. For comparison, Fig. 6a shows the J–V
plots of PEC-cells based on the best responses of ZCIS-QD/TiO2 (SS =
200 μg cm− 2, previous section) and the analogous nanocomposite with
ethanol as co-solvent in the deposition process. Besides the similar trend
already discussed in the previous section, where the Voc, Jsc, and PCE
values were improved by the increase of relative density of ZCIS QDs, a
remarkable effect was verified by the addition of ethanol to the colloidal
solutions (Table 1). Compared to the optimized PEC-cell system (SS =
200 μg cm− 2, no ethanol), enhancements of 165% of Jsc (Figs. 6b), 21%
Fig. 6. (a) J-V curve. (b) Short-circuit current density (JSC). (c) Influence of ethanol as co-solvent in the sensitization of TiO2 electrodes with ZCIS QD colloids. (d)
“OFF-ON” cycle test results of the TiO2 electrodes sensitized with water colloidal ZCIS QDs and with ethanol as co-solvent under “short” and “long” illumination time.
(I) TiO2, (II) ZCIS@CMC_200_350T, and (III) ZCIS@CMC/E_100_350T.
9
Optical Materials 121 (2021) 111557
of Voc, 20% of FF, and 310% of PCE were verified for the samples when
ethanol was used as co-solvent. From the construction of the photoanode
viewpoint, a conceivable explanation for such a big boost by the addi­
tion of co-solvent was accredited to the reduction of the surface tension
of the colloidal solution of ZCIS@CMC nanoconjugates, improving the
percolation, infiltration, and spreading of the fluid throughout the pre-
sintered porous TiO2 film. Moreover, according to few recent studies
[51,52] of QDs as sensitizers for PEC-cells, the destabilization of the
colloids can play an important role in promoting better adsorption onto
TiO2 nanoparticulate films. Therefore, QDs were more evenly and uni­
formly distributed over the nanostructured surface of the TiO2 layer,
which resulted in superior surface area coverage for sensitization
(Fig. 6c).
At the nanoscale level, as discussed in the previous section, these
results of substantial improvement of JV-parameters were ascribed to
better contact between ZCIS QDs and TiO2 nanoparticles, tailoring a
more favorable energy level alignment at the heterojunction interfaces
(i.e., quasi-Fermi level), resulting in a cascade of conduction band edges.
So, when illuminated, the photoexcited carriers of ZCIS QDs travel to the
conduction band of TiO2, which provoked augmented electron flux
throughout the nanostructured assembly followed by the higher flow in
an external electrochemical circuit. Analogously, the improvement of
the charge separation process hindered the exciton recombination
through intermediate electronic states and relaxation pathways, there­
fore improving the overall photovoltaic performance of the cell (e.g., Voc,
FF, Jsc, PCE, Figs. S10–SI). In fact, more recently, the outcomes associ­
ated with the use of co-solvents combined with different QD loading
have been progressively calling the attention of researchers. The com­
plete phenomena taking place are not entirely understood, which are
caused by multiple effects occurring simultaneously at the complex and
dynamic interfaces of the nano-heterojunctions. Moreover, no compa­
rable research was found reporting a similar process developed in this
J.C. Amaral-Júnior et al.
study (ZCIS-QD/TiO2 sensitized PEC-cell) based on water-soluble poly­
mers and sustainable green process [28,42,51–53].
As showed in the previous section regarding the relative density of
sensitizer, corresponding experiments were carried out for assessing the
effect of ethanol used as co-solvent in the photovoltaic activity of the
ZCIS/TiO2 electrode and their stability with time, based on the “light-
ON-OFF” test cycles (cycle of 10 s of light-OFF”; 10 s under “light-ON”,
inset Fig. 6d). Besides the photoconversion activity of the systems under
illumination and relative stability during the 3 cycles, a further
remarkable improvement of the photocurrent density generated of
approximately 160% was observed when ethanol was utilized as co-
solvent compared to the previous optimized system based only on
water (i.e., SS = 200 μg cm− 2, no ethanol). This structure favored a
superior electron flow throughout the entire electrochemical path,
consistent with the literature in analogous quantum dots-based photo­
electrochemical cells [49,50].
Furthermore, in view of the potential application as solar cells, the
stability of the nanostructured system for a longer time under illumi­
nation is also important. Thus, the best PEC-Cell photovoltaic perfor­
mance was chosen (ZCIS QDs/TiO2, ethanol co-solvent, SS = 100 μg
cm− 2) and submitted to a longer cycle of 300 s (Fig. 6d). The results
demonstrated that a very stable PEC-cell system was constructed, where
no chemical or photoinduced degradation through mechanisms of
photooxidation of the nano-heterojunction was observed, considering
that the photocurrent density (~100 μA cm− 2) remained practically
unchanged for the time period investigated. These findings are very
encouraging as far as solar cell applications are concerned, where
multiple cycles associated with long-time stability are required. None­
theless, it should be stated that further studies are required to improve
the photoconversion efficiency parameters comparable to those of
traditionally fabricated solar cell devices relying on commonly toxic
heavy metal materials and not sustainable processes.
4. Conclusions
In this study, the comprehensive strategy of “safe and sustainable by
design (SSD)” was effectively integrated for the development and con­
struction of novel Cu–In–S/ZnS (ZCIS) QD sensitized TiO2 PEC-cells.
ZCIS QDs were produced strictly through an environmentally friendly
colloidal aqueous process at mild conditions, using CMC biopolymer as a
capping ligand and without hazardous or toxicity precursors. The results
demonstrated that uniformly monodispersed ZCIS QDs were produced,
with spherical morphology, chalcopyrite-like crystalline nanostructure,
and an average size of 4.7 nm. Moreover, DLS and ZP analyses showed
the formation of colloids with supramolecular architectures dispersed in
water, predominantly stabilized by electrostatic interactions owing to
the overall balance of charges and molecules in the medium. Regarding
optical properties, the results revealed that the ZCIS-based nanohybrids
presented absorption/emission characteristics with maxima responses
within the visible range of the light spectrum, which is prospectively
suitable for solar-light photoconversion applications. Hence, solid-liquid
junction photoelectrochemical cells (PEC-cell) were fabricated using
TiO2 films deposited onto ITO glass slides sensitized by ZCIS QDs, which
evidenced photoactivity under visible light illumination using “dark”
(“OFF”) and “light” (“ON”) cycles. Moreover, the PEC-cells demon­
strated significant enhancement of photoinduced current density upon
illumination when the relative sensitization density associated with the
ZCIS QDs/TiO2 ratio was increased. The results of considerable
improvement of PV-parameters were ascribed to better contact between
ZCIS QDs and TiO2 nanoparticles, tailoring a more favorable energy
level alignment at the heterojunction interfaces (i.e., quasi-Fermi level),
resulting in a cascade of conduction band edges. Analogously, the use of
ethanol as a co-solvent in the deposition of the ZCIS QDs onto the TiO2
films provoked a remarkable additional increase of over 150% in the
current density. This fact was interpreted as the superior infiltration and
percolation of the colloidal solution through the pre-sintered TiO2 film,
10
Optical Materials 121 (2021) 111557
causing the further enhancement of the coverage and contact between
the 2 semiconductor nanoparticles. To this end, in view of the “SSD”
approach adopted throughout this research, besides relying on green
chemistry colloidal process, nontoxic precursors, and renewable re­
sources, these nanohybrids are biocompatible and eco-friendly. There­
fore, it can be anticipated they are promising candidates as sustainable
photovoltaic cells based on quantum dot-sensitized nanostructures with
tunable optoelectronic properties for constructing clean solar energy
light-harvesting devices in the future.
Funding
The financial support of this research was granted by the Brazilian
Funding Research Agencies: FAPEMIG – Fundação de Amparo à Pes­
quisa do Estado de Minas Gerais (UNIVERSAL-APQ-00291-18; PROBIC-
2018; PPM-00760-16); CAPES - Coordenação de Aperfeiçoamento de
Pessoal de Nível Superior (PROINFRA-2010–2014; PROEX-2010/
2019–2020; PNPD-2014-2019); FINEP - Financiadora de Estudos e
Projetos (CTINFRA/PROINFRA 2008/2010/2011/2018; SOS Equi­
pamentos/2018–01.19.0032.00); CNPq - Conselho Nacional de Desen­
volvimento Científico e Tecnológico (PQ1A-303893/2018–4; PQ1B-
306306/2014–0; PIBIC-2017-18; UNIVERSAL-457537/2014–0;
421312/2018–1; PDS-103138/2020–0); PRPq - Pró Reitoria de Pes­
quisa/UFMG.
CRediT authorship contribution statement
Josué C. Amaral-Júnior: Conceptualization, Methodology, Visual­
ization, Investigation, Formal analysis, Writing – original draft, Writing
– review & editing. Alexandra A.P. Mansur: Conceptualization,
Methodology, Visualization, Investigation, Formal analysis, Writing –
original draft, Writing – review & editing. Isadora C. Carvalho:
Methodology, Visualization, Investigation, Formal analysis, Writing –
original draft, Writing – review & editing. Herman S. Mansur: Super­
vision, Conceptualization, Methodology, Visualization, Validation,
Funding acquisition, Writing – original draft, Writing – review & editing,
Resources, Project administration.
Declaration of competing interest
The authors declare that they have no known competing financial
interests or personal relationships that could have appeared to influence
the work reported in this paper.
Acknowledgments
The authors acknowledge the scientific staff at the Center of Nano­
science, Nanotechnology and Innovation (CeNano2I)/CEMUCASI/
UFMG and the Center of Microscopy/UFMG for the characterization
analyses.
Appendix A. Supplementary data
Supplementary data to this article can be found online at https://doi.
org/10.1016/j.optmat.2021.111557.
References
[1] H. Zhao, F. Rosei, Colloidal quantum dots for solar technologies, Inside Chem. 3
(2017) 229–258, https://doi.org/10.1016/j.chempr.2017.07.007.
[2] X. Li, C. Tung, L. Wu, Semiconducting quantum dots for artificial photosynthesis,
Nat. Rev. Chem. 2 (2018) 160–173, https://doi.org/10.1038/s41570-018-0024-8.
[3] H. Ramsurn, R.B. Gupta, Nanotechnology in solar and biofuels, ACS Sustain. Chem.
Eng. 1 (2013) 779–797, https://doi.org/10.1021/sc400046y.
[4] A.A.P. Mansur, H.S. Mansur, C. Tabare, A. Paiva, N.S.V. Capanema, Eco-friendly
AgInS2/ZnS quantum dot nanohybrids with tunable luminescent properties
modulated by pH-sensitive biopolymer for potential solar energy harvesting
J.C. Amaral-Júnior et al.
applications, J. Mater. Sci. Mater. Electron. 30 (2019) 16702, https://doi.org/
10.1007/s10854-019-00719-0.
[5] X. Wang, C. Liu, C. Gao, K. Yao, S.S.M. Masouleh, R. Berté, H. Ren, L. de
S. Menezes, E. Cortés, I.C. Bicket, H. Wang, N. Li, Z. Zhang, M. Li, W. Xie, Y. Yu,
Y. Fang, S. Zhang, H. Xu, A. Vomiero, Y. Liu, G.A. Botton, S.A. Maier, H. Liang, Self-
constructed multiple plasmonic hotspots on an individual fractal to amplify
broadband hot electron generation, ACS Nano 15 (2021) 10553–10564, https://
doi.org/10.1021/acsnano.1c03218.
[6] H. Zhao, D. Benetti, X. Tong, H. Zhang, Y. Zhou, G. Liu, D. Ma, S. Sun, Z.M. Wang,
Y. Wang, F. Rosei, Efficient and stable tandem luminescent solar concentrators
based on carbon dots and perovskite quantum dots, Nanomater. Energy 50 (2018)
756–765, https://doi.org/10.1016/j.nanoen.2018.06.025.
[7] H. Zhao, R. Sun, Z. Wang, K. Fu, X. Hu, Y. Zhang, Zero-dimensional perovskite
nanocrystals for efficient luminescent solar concentrators, Adv. Funct. Mater. 29
(2019) 1902262, https://doi.org/10.1002/adfm.201902262.
[8] C.W. Babbitt, E.A. Moore, Sustainable nanomaterials by design, Nat. Nanotechnol.
13 (2018) 621–623, https://doi.org/10.1038/s41565-018-0235-7.
[9] M.M. Falinski, D.L. Plata, S.S. Chopra, T.L. Theis, L.M. Gilbertson, J.B. Zimmerman,
A framework for sustainable-nanomaterial selection and design based on
performance, hazard, and economic considerations, Nat. Nanotechnol. 13 (2018)
708–714, https://doi.org/10.1038/s41565-018-0120-4.
[10] P. Anastas, N. Eghbali, Green chemistry: principles and practice, Chem. Soc. Rev.
39 (2010) 301–312, https://doi.org/10.1039/B918763B.
[11] D. Aldakov, P. Reiss, Safer-by-design fluorescent nanocrystals: metal halide
perovskites vs. semiconductor quantum dots, J. Phys. Chem. C 123 (2019), https://
doi.org/10.1021/acs.jpcc.8b12228, 12527− 21254.
[12] Y. Yang, Y. Zheng, W. Cao, A. Titov, J. Hyvonen, J.R. Manders, J. Xue, P.
H. Holloway, L. Qian, High-efficiency light-emitting devices based on quantum
dots with tailored nanostructures, Nat. Photonics 9 (2015) 259–266, https://doi.
org/10.1038/nphoton.2015.36.
[13] F. Meinardi, H. McDaniel, F. Carulli, A. Colombo, K.A. Velizhanin, N.S. Makarov,
R. Simonutti, V.I. Klimov, S. Brovelli, Highly efficient large-area colourless
luminescent solar concentrators using heavy-metal-free colloidal quantum dots,
Nat. Nanotechnol. 10 (2015) 878–885, https://doi.org/10.1038/nnano.2015.178.
[14] B. Bai, D. Kou, W. Zhou, Z. Zhou, S. Wu, Application of quaternary Cu2ZnSnS4
quantum dot sensitized solar cells based on the hydrolysis approach, Green Chem.
17 (2015) 4377–4382, https://doi.org/10.1039/C5GC01049G.
[15] H.S. Mansur, Quantum dots and nanocomposites, WIREs Nanomed.
Nanobiotechnol. 2 (2010) 113–129, https://doi.org/10.1002/wnan.78.
[16] H.S. Mansur, A.A.P. Mansur, Amanda Soriano-Araújo, Z.I.P. Lobato, Beyond
biocompatibility: an approach for the synthesis of ZnS-quantum dot/chitosan
nanoimmunoconjugates for cancer diagnosis, Green Chem. 17 (2015) 1820–1830,
https://doi.org/10.1039/C4GC02072C.
[17] F.P. Ramanery, A.A.P. Mansur, L.C. Oliveira, H.S. Mansur, Carboxymethyl chitosan
functionalization of Bi2S3 quantum dots: towards eco-friendly fluorescent core-
shell nanoprobes, Carbohydr. Polym. 146 (2016) 455–466, https://doi.org/
10.1016/j.carbpol.2016.03.062.
[18] D.B. Choi, S. Kim, H.C. Yoon, M. Ko, H. Yang, Y.R. Do, Color-tunable Ag-In-Zn-S
quantum-dot light-emitting devices realizing green, yellow and amber emissions,
J. Mater. Chem. C 5 (2017) 953–959, https://doi.org/10.1039/C6TC04798J.
[19] S.M. Kobosko, P.V. Kamat, Indium-rich AgInS2–ZnS quantum dotsAg-/Zn-
dependent photophysics and photovoltaics, J. Phys. Chem. C 122 (2018)
14336–14344, https://doi.org/10.1021/acs.jpcc.8b03001.
[20] S. Raveendran, A.R. Girija, S. Balasubramanian, T. Ukai, Y. Yoshida, T. Maekawa,
D.S. Kumar, Green approach for augmenting biocompatibility to quantum dots by
extremophilic polysaccharide conjugation and nontoxic bioimaging, ACS Sustain.
Chem. Eng. 2 (2014) 1551–1558, https://doi.org/10.1021/sc500002g.
[21] G. Xu, S. Zeng, B. Zhang, M.T. Swihart, K.-T. Yong, P.N. Prasad, New generation
cadmium-free quantum dots for biophotonics and nanomedicine, Chem. Rev. 116
(2016) 12234–12327, https://doi.org/10.1021/acs.chemrev.6b00290.
[22] M.A. Abate, K. Dehvari, J.-Y. Chang, K. Wakic, Aqueous synthesis of Mn-doped
CuInSe2 quantum dots to enhance the performance of quantum dot sensitized solar
cells, Dalton Trans. 48 (2019) 16115–16122, https://doi.org/10.1039/
C9DT03163D.
[23] D. Sharma, R. Jha, S. Kumar, Quantum dot sensitized solar cell: recent advances
and future perspectives in photoanode, Sol. Energy Mater. Sol. Cells 155 (2016)
294–322, https://doi.org/10.1016/j.solmat.2016.05.062.
[24] A. Sahu, A. Garg, A. Dixit, A review on quantum dot sensitized solar cells: past,
present and future towards carrier multiplication with a possibility for higher
efficiency, Sol. Energy 203 (2020) 210–239, https://doi.org/10.1016/j.
solener.2020.04.044.
[25] Y.-C. Chen, H.-H. Chang, Y.-K. Hsu, Synthesis of CuInS2 quantum dots/In2S3/ZnO
nanowire arrays with high photoelectrochemical activity, ACS Sustain. Chem. Eng.
6 (2018) 10861–10868, https://doi.org/10.1021/acssuschemeng.8b02154.
[26] P. Ilaiyaraja, B. Rakesh, T.K. Das, P.S.V. Mocherla, C. Sudakar, CuInS2 quantum dot
sensitized solar cells with high VOC ≈ 0.9 V achieved using microsphere-
nanoparticulate TiO2 composite photoanode, Sol. Energy Mater. Sol. Cells 178
(2018) 208–222, https://doi.org/10.1016/j.solmat.2018.01.018.
[27] A. Raevskaya, O. Rosovik, A. Kozytskiy, O. Stroyuk, V. Dzhagan, D.R.T. Zahn, Non-
stoichiometric Cu–In–S@ZnS nanoparticles produced in aqueous solutions as light
harvesters for liquid-junction photoelectrochemical solar cells, RSC Adv. 6 (2016)
100145–100157, https://doi.org/10.1039/C6RA18313A.
[28] S. Higashimoto, T. Nakase, S. Mukai, M. Takahashi, Copper-indium-sulfide colloids
on quantum dot sensitized TiO2 solar cell: effects of capping with mercapto-acid
linker molecules, J. Colloid Interface Sci. 535 (2019) 176–181, https://doi.org/
10.1016/j.jcis.2018.09.092.
11
Optical Materials 121 (2021) 111557
[29] A.S. Fuhr, H.J. Yun, N.S. Makarov, H. Li, H. McDaniel, V.I. Klimov, Light emission
mechanisms in CuInS2 quantum dots evaluated by spectral electrochemistry, ACS
Photonics 4 (2017) 2425–2435, https://doi.org/10.1021/acsphotonics.7b00560.
[30] J.C. Amaral-Júnior, A.A.P. Mansur, I.C. Carvalho, H.S. Mansur, Tunable-
luminescence of CuInS/ZnS quantum dots/polysaccharide nanohybrids by
environmentally friendly synthesis for potential solar energy photoconversion
applications, Appl. Surf. Sci. 542 (2021) 148701, https://doi.org/10.1016/j.
apsusc.2020.148701.
[31] H. Wang, J. Hu, M. Zhu, Y. Li, H. Qian, X. Shen, F. Liebner, T. Rosenau, Full-color-
emitting (CuInS2)ZnS-alloyed core/shell quantum dots with trimethoxysilyl end-
capped ligands soluble in an ionic liquid, RSC Adv. 9 (2019) 25576–25582,
https://doi.org/10.1039/C9RA03066B.
[32] A. Raevskaya, O. Rozovik, A. Novikova, O. Selyshchev, O. Stroyuk, V. Dzhagan,
I. Goryacheva, N. Gaponik, D.R.T. Zahn, A. Eychmüller, Luminescence and
photoelectrochemical properties of size-selected aqueous copper-doped Ag–In–S
quantum dots, RSC Adv. 8 (2018) 7550–7557, https://doi.org/10.1039/
C8RA00257F.
[33] A.A.P. Mansur, F.G. de Carvalho, R.L. Mansur, S.M. Carvalho, L.C. de Oliveira, H.
S. Mansur, Carboxymethylcellulose/ZnCdS fluorescent quantum dot
nanoconjugates for cancer cell bioimaging, Int. J. Biol. Macromol. 96 (2017)
675–686, https://doi.org/10.1016/j.ijbiomac.2016.12.078.
[34] M. Bundschuh, J. Filser, S. Lüderwald, M.S. McKee, G. Metreveli, G.E. Schaumann,
R. Schulz, S. Wagner, Nanoparticles in the environment: where do we come from,
where do we go to? Environ. Sci. Eur. 30 (2018) 6, https://doi.org/10.1186/
s12302-018-0132-6.
[35] A.G. Leonel, A.A.P. Mansur, H.S. Mansur, Advanced functional nanostructures
based on magnetic iron oxide nanomaterials for water remediation: a review,
Water Res. 190 (2021) 116693, https://doi.org/10.1016/j.watres.2020.116693.
[36] N. Oh, J.-H. Park, Endocytosis and exocytosis of nanoparticles in mammalian cells,
Int. J. Nanomed. 9 (2014) 51–63, https://doi.org/10.2147/IJN.S26592.
[37] M. Katerji, M. Filippova, P. Duerksen-Hughes, Approaches and methods to measure
oxidative stress in clinical samples: research applications in the cancer field, Oxid.
Med. Cell. Longevity 2019 (2019) 1279250, https://doi.org/10.1155/2019/
1279250.
[38] D. Britto, O.B.G. Assis, Thermal degradation of carboxymethylcellulose in different
salty forms, Thermochim. Acta 494 (2009) 115–122, https://doi.org/10.1016/j.
tca.2009.04.028.
[39] M. Akram, I. Taha, M.M. Ghobashy, Low temperature pyrolysis of
carboxymethylcellulose, Cellulose 23 (2016) 1713–1724, https://doi.org/
10.1007/s10570-016-0950-x.
[40] H.S. Mansur, F. Grieser, M.S. Marychurch, S. Biggs, R.S. Urquhart, D.N. Furlong,
Photoelectrochemical properties of ‘Q-state’ CdS particles in arachidic acid
Langmuir–Blodgett films, J. Chem. Soc., Faraday Trans. 91 (1995) 665–672,
https://doi.org/10.1039/FT9959100665.
[41] H.S. Mansur, F. Grieser, R.S. Urquhart, D.N. Furlong, Photoelectrochemical
behaviour of Q-state CdSxSe(1 –x) particles in arachidic acid Langmuir–Blodgett
films, J. Chem. Soc., Faraday Trans. 91 (1995) 3399–3404, https://doi.org/
10.1039/FT9959103399.
[42] Y.-H. Chiang, K.-Y. Lin, Y.-H. Chen, K. Waki, M.A. Abate, J.-C. Jiang, J.-Y. Chang,
Aqueous solution-processed off-stoichiometric Cu–In–S QDs and their application
in quantum dot-sensitized solar cells, J. Mater. Chem. 6 (2018) 9629–9641,
https://doi.org/10.1039/c8ta01064a.
[43] C. Ng, J.-H. Yun, H.L. Tan, H. Wu, R. Amal, Y.H. Ng, A dual-electrolyte system for
photoelectrochemical hydrogen generation using CuInS2-In2O3-TiO2 nanotube
array thin film, Sci. China Mater. 64 (2018) 895–904, https://doi.org/10.1007/
s40843-017-9237.
[44] P.K. Santra, P.V. Nair, K.G. Thomas, P.V. Kamat, CuInS2-sensitized quantum dot
solar cell. electrophoretic deposition, excited-state dynamics, and photovoltaic
performance, J. Phys. Chem. Lett. 4 (2013) 722–729, https://doi.org/10.1021/
jz400181m.
[45] P.V. Kamat, Quantum-dot solar cells. semiconductor nanocrystals as light-
harvesters, J. Phys. Chem. C 112 (2008) 18737–18753, https://doi.org/10.1021/
jp806791s.
[46] M.S. Ahmad, A.K. Pandey, N.A. Rahim, Advancements in the development of TiO2
photoanodes and its fabrication methods for dye sensitized solar cell (DSSC)
applications. A review, Renew. Sustain. Energy Rev. 77 (2017) 89–108, https://
doi.org/10.1016/j.rser.2017.03.129.
[47] R.N. Gayen, T. Chakrabarti, Effect of series and shunt resistance on the
photovoltaic properties of solution-processed zinc oxide nanowire based CZTS
solar cell in superstrate configuration, Mater. Sci. Semicond. Process. 100 (2019)
1–7, https://doi.org/10.1016/j.mssp.2019.04.018.
[48] R.E. Brandt, N.M. Mangan, J.V. Li, Y.S. Lee, T. Buonassisi, Determining interface
properties limiting open-circuit voltage in heterojunction solar cells, J. Appl. Phys.
121 (2017) 185301, https://doi.org/10.1063/1.4982752.
[49] X. Tong, A.I. Channa, Y. You, P. Wei, X. Li, Feng Lin, J. Wu, A. Vomiero, Z.
M. Wang, Boosting the performance of eco-friendly quantum dots-based
photoelectrochemical cells via effective surface passivation, Nanomater. Energy 76
(2020) 105062, https://doi.org/10.1016/j.nanoen.2020.105062.
[50] X. Su, Y. Chen, L. Ren, Y. He, X. Yin, Y. Liu, W. Yang, Cobalt catalyst grafted
CdSeTe quantum dots on porous NiO as photocathode for H2 evolution under
visible light, ACS Sustain. Chem. Eng. 7 (2019) 11166–11174, https://doi.org/
10.1021/acssuschemeng.9b00305.
J.C. Amaral-Júnior et al.
[51] J.-H. Kim, S. Bae, B.K. Min, Impact of absorber layer morphology on photovoltaic
properties in solution-processed chalcopyrite solar cells, ACS Appl. Mater.
Interfaces 13 (2021) 34–47, https://doi.org/10.1021/acsami.0c17496.
[52] W. Wang, H. Rao, W. Fang, H. Zhang, M. Zhou, Z. Pan, X. Zhong, Enhancing
loading amount and performance of quantum-dot-sensitized solar cells based on
12
Optical Materials 121 (2021) 111557
direct adsorption of quantum dots from bicomponent solvents, J. Phys. Chem. Lett.
10 (2019) 229–237, https://doi.org/10.1021/acs.jpclett.8b03713.
[53] D. Zhang, S. Zhang, Y. Fang, D. Xie, X. Zhou, Y. Lin, Effect of linkers with different
chemical structures on photovoltaic performance of CdSe quantum dot-sensitized
solar cells, Electrochim. Acta 367 (2021) 137452, https://doi.org/10.1016/j.
electacta.2020.137452.