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Low-temperature processing of optimally polymer-wrapped α-CsPbI3 for

self-powered flexible photo-detector application

Article in Journal of Materials Chemistry C · May 2019

DOI: 10.1039/C9TC01292C

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Low-temperature processing of optimally

polymer-wrapped a-CsPbI3 for self-powered
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Cite this: J. Mater. Chem. C, 2019,

7, 6986 flexible photo-detector application†
Umesh Bansode, Atikur Rahman* and Satishchandra Ogale *

Received 7th March 2019,
Accepted 7th May 2019
DOI: 10.1039/c9tc01292c
rsc.li/materials-c
For the application of a-CsPbI3 in optoelectronic devices, low-temperature processability and high
environmental stability are critically important. Herein, we have grown a polyvinylpyrrolidone (PVP)
polymer-wrapped highly stable cubic phase (a) of CsPbI3 at low temperature (60 1C) using a single step
spin coating method. The optimal quantity of PVP critically facilitates precursor diffusion to form the
desired phase at low temperature and concurrently renders stability to the phase. A photo-detector
using a heterostructure of CsPbI3 and SnO2 on a flexible substrate is demonstrated, operating over the
broad wavelength range 400–700 nm in a self-powered mode. The on/off photocurrent ratio of this
self-powered flexible device is 4103. The average responsivity, external quantum efficiency, and
detectivity of the device are around 100 mA W 1, 25%, and 1012 Jones, respectively. The noise current of
1/2
our device is 15 pA Hz under dark conditions (at 50 mV bias) at 117 Hz frequency. The rise/fall times
of the photo-detector are found to be 5.7/6.2 ms, respectively; thus showing an ultrafast response. This
self-powered flexible photo-detector shows very good stability even after 500 bending cycles.

Introduction challenges like phase segregation in mixed halide hybrid

Semiconductor photodetectors have broad ranging applications
in optical communication, telecommunication, security checking,
consumer electronics, imaging techniques, industry, defense, and
academic research.1–5 The desirable properties of an efficient
photodetector include low dark and noise current, high respon-
sivity, detectivity, and light on/off ratio, low noise equivalent
power, and ultrafast photo-response.6 With rapid growth of the
fields of wearable electronics and the internet of things (IOT),
interest in flexible photodetectors is also growing rapidly.
Recently, organic–inorganic hybrid perovskites have been
intensely researched as highly promising photoactive materials
for next generation optoelectronic devices due to their excep-
tional properties such as high absorption coefficient (105 cm 1)
over a broad range of wavelengths, high diffusion length
(41 mm), band gap tunability by a mixed halide approach,
and simple solution processability at low temperature.7–11
Unfortunately, these materials suffer from instability issues
due to their property sensitivity to moisture, temperature and
UV illumination.12,13 Moreover, there are still unresolved
Department of Physics and Centre for Energy Science, Indian Institute for Science
Education and Research, Dr. Homi Bhabha Road, Pune 411008, India.
E-mail: satishogale@iiserpune.ac.in, atikur@iiserpune.ac.in
† Electronic supplementary information (ESI) available. See DOI: 10.1039/
c9tc01292c
perovskites under illumination.14 Some of these issues
(thermal stability, moisture stability etc.) can be addressed
differently in certain inorganic halide perovskites. As such,
interest has grown in exploring their use in different optoelec-
tronic applications including tandem solar cells with silicon.15
Amongst all the inorganic halide perovskites the cubic phase
a-CsPbI3 is perhaps the most interesting candidate in this
respect due to its significantly high thermal stability
(4300 1C), and the right band gap of 1.73 eV, essential for
tandem solar cells with silicon. The processing temperature to
form the cubic a-CsPbI3 phase is 4300 1C.15–18 However, it is
thermodynamically unstable at room temperature and gets
converted to the yellow non-perovskite d-phase (2.3 eV).15,19
Unfortunately, the a-phase is also highly sensitive to moisture,
getting converted to the d form. Thus, it is a challenge to
process the a-phase at low temperature and disallow its phase
transformation at room temperature.
There have been several attempts to stabilize the a-phase of
CsPbI3 using polymer functionalization, metal ion doping,
organic molecule additives/surface treatment, hydroiodide
(HI) addition, and mixed halide (Br/I) alloying.19–30 The mixed
halide approach could stabilize the cubic phase of CsPbI3 but
this increased the band gap to 1.92 eV due to the bromine
content.18,31–34 Another approach to stabilize the cubic phase of
CsPbI3 is by employing its quantum dot/nanoparticle form
stabilized by using long chain organic ligands.35–38 However,

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this approach introduces a lot of grain boundaries due to small
grains during the fabrication of devices, which reduce the
charge transfer rate and increase the carrier recombination.
Thus, to maintain the a-form for long periods under ambient
conditions in real world applications is a real challenge.
The other black phases of CsPbI3 are the tetragonal (b) and
orthorhombic (g) phases, having distorted octahedra in a 3D
configuration. These phases are metastable and are called
perovskitoids. They occur during the transition of CsPbI3 from
the non-perovskite d-CsPbI3 phase to a-CsPbI3. The b and g
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phases of CsPbI3 have been demonstrated in photovoltaic
devices with a power conversion efficiency of 5% and 11%
respectively.39,40 Recently, a a-CsPbI3 based solar cell has been
shown to render a power conversion efficiency (PCE) of 17%
wherein the cubic phase was stabilized using post-treatment of
phenyltrimethylammonium bromide; but the stability of the
devices was noted to be low in an ambient atmosphere.41
In the work reported here, we have successfully stabilized the
cubic phase of CsPbI3 at a low temperature of only 60 1C by
employing polyvinylpyrrolidone (PVP) wrapping, using a single step
spin coating process. The key was to use an optimum quantity of
the PVP wrapper polymer as discussed later in the text. Facilitated
by the low temperature process, we also fabricated a flexible
photodetector using an ITO/SnO2/CsPbI3/Au configuration on a
flexible PET substrate. This device operated in a self-powered
mode, giving an impressive response in the broad visible region
(400–700 nm) of the electromagnetic spectrum. The on/off photo-
current ratio of this self-powered flexible device was around 103,
while its specific detectivity was 1012 Jones. The noise current of our
device was 15 pA Hz 1/2 under dark conditions (at 50 mV bias) at
117 Hz frequency. The rise/fall times of the CsPbI3 based photo-
detector were found to be 5.7 and 6.2 ms, respectively; thus exhibiting
a fast response. Moreover, this self-powered flexible photodetector
showed very good stability even after 500 bending cycles.
Experimental section
Chemicals
CsI (99.9%, Sigma-Aldrich), PbI2 (99.9%, Alfa-Aesar), polyvinyl-
pyrrolidone (Sigma-Aldrich), polyethylene oxide, N,N-dimethyl-
formamide (anhydrous, Sigma-Aldrich), dimethyl sulfoxide
(anhydrous, Sigma-Aldrich), and SnO2 (15%, Alfa-Aesar) chemicals
were used as received without any further purification.
A CsPbI3 solution was prepared by dissolving 259 mg of CsI
(Sigma-Aldrich) and 460 mg of PbI2 (Alfa-Aesar) in a mixture of
N,N-dimethyl formamide (DMF) and dimethyl sulfoxide
(DMSO) (1 ml DMSO + 0.4 ml of DMF) with stirring in an
argon-filled glove box. 50 mg of polyvinylpyrrolidone (PVP) was
weighed and dissolved in 1.35 ml of the above (CsPbI3) solution
with constant stirring. A polyethylene oxide (PEO) based
solution was prepared by dissolving PEO in the CsPbI3 solution.
Device fabrication
ITO-PET substrates were etched using zinc metal powder and
diluted hydrochloric acid. The etched substrates were cleaned
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using sequential sonication in a soap solution, distilled water,
and 2-propanol for 15 minutes each. The substrates were
further cleaned using plasma cleaning in an oxygen atmo-
sphere. A SnO2 solution was prepared by diluting commercially
available SnO2 solution (15% colloidal dispersion from
Alfa-Aesar) with distilled water in a 1 : 3 ratio. SnO2 was spin
coated on the plasma treated substrates at 3000 rpm for
30 seconds followed by annealing at 120 1C for 30 minutes.
The samples were allowed to cool and were transferred to a
glove box for perovskite deposition. The perovskite solution was
spin coated at 3000 rpm for 30 seconds and heated at 60 1C for
5 minutes. Finally, gold was thermally evaporated on the top of
the perovskite using a shadow mask.
Photodetector device measurement
We used a 300 W Xe lamp as a light source passing through a
monochromatic unit to select specific wavelengths of incident
light. The light on/off experiment was carried out by using a
mechanical chopper. The I–V and I–T measurements were
carried out using a Keithley 2612 meter. The power of the
incident light was measured using a Newport power-meter. The
power of the incident light was reduced by using neutral
density filters.
Transient measurement
The transient measurement was done with various frequencies
(100 Hz to kHz) and a LED light source with a wavelength of
500 nm (the rise/fall time for the LED is 14 ns) and the pulse
width was varied from 30–100 ms. The device was operated in
self-bias mode and the signal was recorded with the help of
an oscilloscope. The frequency of the light was varied using a
function generator.
Noise current measurement
The noise current measurement was carried out using a pre-
amplifier (Stanford Research Systems, SR570). For the noise
study, the current measurement device was kept under a
0.50 V reverse bias condition in the dark with a 0.1–1000 Hz
frequency range.
Results and discussion
According to the previous reports, amongst all the a, b, and g
black phases of the CsPbI3 system, the g phase occurs at low
temperature around 60 1C, while b and a occur at 237 1C and
310 1C, respectively.42 The g-CsPbI3 phase is a perovskite
polymorph having high defect tolerance with a band gap of
around 1.7 eV and crystallizes at low temperature. It can
potentially be used for flexible optoelectronic applications,
however its stability is a major issue, due to its high surface
energy. Its sustainability has only been achieved by increasing
the surface area by decreasing the size of the grains up to
100 nm.39
For making the thin films of CsPbI3 in our case, we initially
used a solution of CsPbI3 (0.75 M) in a mixture of DMF–DMSO
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Fig. 1 X-ray diffraction patterns of (a) g-CsPbI3 experimental and simulated (inset shows a black film inside the polycarbonate dome XRD sample
holder); (b) d-CsPbI3 experimental and simulated (inset shows a yellow tinge on the film inside the polycarbonate dome XRD sample holder); and
(c) a-CsPbI3 experimental and simulated (brown black color film).
(without any polymer involvement). This solution was spin-
coated on a cleaned glass substrate in an inert atmosphere and
the films were heated at 60 1C. The films started turning from
yellow to black within a minute. We noticed that the black films
could not maintain their phase and converted to the yellow
non-perovskite form even in an inert atmosphere within an
hour. To check the structural form of the black phase, we
performed XRD of the fresh sample instantly, with a polycar-
bonate dome XRD sample holder. Fig. 1(a) shows the XRD of
the CsPbI3 measured immediately after film preparation. The
inset of Fig. 1(a) shows the polycarbonate dome of the XRD
sample holder, containing the black coloured film. The X-ray
diffraction pattern (Fig. 1(a) red curve) perfectly matches with
the previously reported data for g-CsPbI3 (i.e. the simulated
X-ray diffraction pattern of g-CsPbI3 using the CIF file of a
previous report with the help of Vesta software).39,42,43 g-CsPbI3
is formed at 60 1C due to the inter-diffusion of Cs ions into the
PbI2 matrix.40 g-CsPbI3 is the distorted orthorhombic form of
the perovskite, as shown in the Fig. 1(a) inset, where the
[PbI6]4 octahedra are tilted at an angle of 155.61, lowering
the symmetry. In the XRD of g-CsPbI3, the peaks around 141,
211, 281, and 421 are all seen to have split due to the distorted
structure shown in the Fig. 1(a) inset. The lattice parameters for
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g-CsPbI3 are as follows: a = 8.646 Å, b = 8.818 Å, and c = 12.520 Å,
along with an angle of 155.61 for the Pb–I–Pb bond, and the space
group is Pbnm.39,42,43
We performed an XRD measurement for the same sample
after an hour, under similar conditions (in a polycarbonate
dome). The color of the film turned from black to yellow as
shown in the photograph inset of Fig. 1(b). The g-CsPbI3 thus
got converted to its most stable thermodynamic phase d-CsPbI3
(space group pnma). According to a previous report, without any
treatment/additive, g-CsPbI3 is thermodynamically less stable
than d-CsPbI3, due to which the phase transformation occurs.39
The XRD of d-CsPbI3, the crystal structure and the photograph
of the film (inside the XRD sample holder) are shown in
Fig. 1(b). The XRD pattern of the d-CsPbI3 very well matched
with the simulated XRD as well as that in a previous report.42,43
The XRD pattern was simulated from the previous reported
CIF file.42
Polyvinylpyrrolidone (PVP) has been demonstrated as a
surface functionalization agent for CsPbI3 nanoparticles (NPs).24,44
During the nucleation and growth process of CsPbI3 NPs, the
PVP molecule approaches the positive charge of CsPbI3 pre-
cursors with a long backbone chain having the electronegative
acylamino group. With increasing time the PVP molecule wraps
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the CsPbI3 surface and stops the growth to form the nano-
particles.24 In their interesting work, Yin and co-workers24 used
10 wt% PVP in CsPbI3 solution and spin coated on the film. The
film was then heated at 300 1C for 5 minutes. After cooling they
dipped it in an IPA solution for 30 minutes to remove the
redundant PVP. We realized in our experiments that use of a
high concentration of PVP required higher temperature for
radical diffusion and phase formation and post-heating
removal of PVP led to lower than optimum conductivity. As
discussed by Yin and co-workers,24 since PVP essentially wraps
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the grains via the electronegative acylamino groups, and
protects and stabilizes the desired cubic phase, it is best to
add a much lower quantity of PVP to achieve phase formation
at lower temperature and good conductivity by skipping the
step of removal of redundant PVP. This trick worked when we
added about 3.5 wt% PVP into the CsPbI3 solution and spin
coated the film with immediate heating at 60 1C. Interestingly,
the films appeared black-brown in color within a minute. Most
importantly, the films were found to be stable in ambient
atmosphere for a long time without any phase change, perfectly
suitable for growth on flexible polymeric substrates.
We performed an XRD measurement for the fabricated film
and the result is shown in Fig. 1(c). It shows the XRD pattern for
the PVP-CsPbI3 case (blue curve), simulated XRD of a-CsPbI3
(from the previous reported CIF file),42 a photograph showing
the black film, and the crystal structure of the a-CsPbI3.
Importantly, in this case, the XRD pattern reflects the a-CsPbI3
phase and not the g-CsPbI3. There is no splitting of any peak of
the XRD pattern of the PVP-CsPbI3 case, which reflects that there
is no distortion due to the tilting of [PbI6]4 octahedra. This
confirmed that the phase of PVP functionalized CsPbI3 is cubic.
Interestingly, we achieved the a-CsPbI3 at a very low temperature
of 60 1C with much better stability even under ambient condi-
tions. For the nucleation process the Cs insertion and the corner
sharing arrangement of the [PbI6]4 octahedra are important,
which occur at 60 1C, while PVP stabilizes the cubic phase through
the functionalization.
The XRD peaks of the PVP-CsPbI3 film case are broad,
reflecting a smaller grain size. We calculated the crystallite size
using the Scherrer formula, which is close to 15 nm. To study
the effect of the processing temperature on the evolution of the
PVP-CsPbI3 film, we heated the films with various temperatures
over the range from 80 to 150 1C. The XRD patterns for the
same films are included in Fig. S1(a) (ESI†). The XRD line width
decreases with an increase in the processing temperature from
80–150 1C. This result reflects the increase in the crystallite size
with increasing processing temperature.
We also examined another polymer functionality, namely
polyethylene oxide (PEO), for the growth of a-CsPbI3 at low
temperature. For this, we added PEO to the CsPbI3 precursor
solution instead of PVP. The solution was spin coated on a glass
substrate and heated at 60 1C in an inert atmosphere. Fig. S1(b)
(ESI†) shows the XRD pattern of the PEO-CsPbI3 case, which also
shows the cubic phase CsPbI3. We however used only PVP-CsPbI3
for the optoelectronic study due to its high stability in ambient
atmosphere as compared to PEO-CsPbI3. Comparatively, PEO is
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more hydrophilic in nature, and grabs water molecules and
reduces the a phase stability.45
Field emission scanning electron microscopy (FE-SEM)
images were recorded for the evaluation of the morphology of
the PVP-CsPbI3 films and these are shown in Fig. 2(a). The grain
size of the perovskite is found to be around 100–120 nm. These
grains are however seen to be formed by aggregation of the
small nanoparticles, as reflected in Fig. S2(a) (ESI†).
To evaluate the size and the morphology of these aggregated
nanoparticles, we performed transmission electron microscopy
(TEM) imaging by scratching out CsPbI3 powder from the film.
Fig. S2(b) (ESI†) shows the TEM images of the a-CsPbI3, where
we found particles with sizes in the range 12–20 nm. The lattice
fringes revealed an interplanar distance of 2.82 Å, which
corresponds to the (210) plane.
To evaluate the optical response of the PVP-CsPbI3 films, we
carried out an absorbance and photoluminescence study. The
absorption band edge of PVP-CsPbI3 is seen around 700 nm,
which corresponds to a band gap of 1.77 eV.
A time-resolved photoluminescence (TRPL) measurement
(Fig. 2(d)) was carried out to investigate the lifetime in the case
of PVP-CsPbI3. The PL decay for the PVP-CsPbI3 film exhibits a
time constant of t = 33.5 ns. The PL decay curve was fitted with
a tri-exponential function, and the parameters and the relative
contribution data are included in the ESI† (Table S1). As per a
previous report, as the particle size increases the lifetime
increases.37
Since the PVP-CsPbI3 system has broad-band absorption in
the visible region, a low film processing temperature, and a
better carrier life-time, we decided to fabricate a photodetector
based on this material on a flexible substrate. In this photo-
detector, we used ITO coated PET as a flexible substrate on
which a hetero-junction of SnO2 and PVP-CsPbI3 was prepared
by a solution process; and gold was deposited as the top
electrode using thermal evaporation. SnO2 is an n-type semi-
conductor with high electron mobility and, according to
theoretical study, CsPbI3 is a p-type semiconductor; hence the
heterojunction was envisioned to serve as a photodetector.46,47
Fig. 3(a) shows the schematic diagram of our device we per-
formed dark and light I–V (sweep voltage from 0.5 to +0.5)
measurements; the corresponding results are shown in
Fig. 3(b). Since the heterojunction of SnO2 and CsPbI3 is a
p–n junction, it shows the expected diode characteristics. The
I–V curve in Fig. 3(b) is like a p–n junction solar cell. The black
curve is the I–V for the dark, and blue is the one under
illumination. The device clearly showed a significant change
under illumination with a 450 nm wavelength. Importantly,
although PVP is an insulating polymer,45 its optimum use as
one or a few monolayers wrapped around the semiconducting
CsPbI3 nanograins renders desirable conductivity via a tunnel-
ing process, stabilizes the cubic phase, and also gives an
impressive photocurrent. The breakdown voltage for our device
was around 0.42 V (in the dark) under reverse bias. The
breakdown voltage was 0.37 V for the photodetector under
the illumination condition. The reduction in the breakdown
voltage under illumination with light can be attributed to the
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Fig. 2 (a) FE-SEM image of the a-CsPbI3 film, (b) EDAX pattern, (c) absorption and steady state PL spectra of a-CsPbI3, and (d) photoluminescence
relaxation data for the a-CsPbI3 film probed at 400 nm.
reduction in the depletion width (enhancement in the carrier
concentration in the depletion region upon incident light) of
the p–n junction. As CsPbI3 has broad-band absorption with a
band edge around 700 nm, it is potentially useful for broad-
band photodetector applications. Interestingly the device
shows a very good response even at 0 V, as shown in the inset
of Fig. 3(b). The device thus works in a self-bias mode due to
the appropriate band alignment, which is shown in Fig. 3(c).
Fig. 4(a) shows current density ( J) vs. time (t) of the photo-
detector under light on and off cycles at 0 bias, for different
wavelengths in the range of 400–700 nm. Our device showed an
exceptionally impressive photoresponse with an on/off ratio
greater than 1.8  103 for different wavelengths in the range
from 400 to 650 nm, at an intensity of light o70 mW cm 2. The
light on/off ratio even for the near band edge wavelength of
700 nm is around 3  102.
The responsivity and detectivity are very important para-
meters which define the efficiency of the device in an actual
application. Fig. 4(b) shows the responsivity and detectivity of
the detector for different wavelengths. The responsivity was
calculated using the following formula,48
R = (Ilight Idark)/(power density  area)
The dark current of our device is 1.5  10 9 A, the power density
for various wavelengths is included in the ESI† (Table S2), and the
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illumination area was 0.06 cm2. The responsivity and detectivity
of the device were measured/calculated under the 0 bias
(self-powered) condition.
Another important parameter for the photodetector is the
specific detectivity, which can be calculated according to the
following formula49
D* = (ROA)/O((2q
Idark))
where D* is the specific detectivity, R is the responsivity, A is the
device active area, q is the electrical charge, and Idark is the dark
current. Very interestingly, our device showed a specific detec-
tivity around 1  1012 Jones (cm Hz1/2 W 1), which for the
wavelength range of 400–650 nm is comparable with silicon-
based photodetectors.50,51 The high specific detectivity of the
PVP-CsPbI3 film based flexible photo-detector indicates that it
can detect a very low intensity of light. Notably, in contrast to
the case of the material and work presented here, it is very
difficult to fabricate a Si-based photo-detector on a flexible
substrate due to its high processing temperature and brittleness.
The specific detectivity in our case was however somewhat less for
the wavelength 700 nm, around 2.5  1011 Jones. The responsivity
and specific detectivity mostly follow the absorption spectra of the
active material. To evaluate the photoresponse of the device at
minimum illumination power, we reduced the intensity of light
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Fig. 3 (a) Schematic of the flexible photodetector, (b) I–V in the dark and under illumination at 450 nm, and (c) representation of the band alignment.
further using neutral density filters from the range of microwatts
to nanowatts.
The J–T profile as a function of the light intensity at a
wavelength of 650 nm is shown in Fig. 4(c). The device showed
around a one order of magnitude on/off ratio even under a light
intensity of 43.5 nW. This establishes that our device gives
almost a one order of magnitude photoresponse even with a
few nW level of illumination. Fig. 4(d) shows the photocurrent
and calculated responsivity as a function of the intensity of the
light illumination. The photocurrent is seen to increase almost
linearly with the increase in the intensity of the light, while the
responsivity of the device is seen to slightly decrease. It follows
the trend in perovskite-based photodetector devices as per
earlier reports.51–56 The responsivity is seen to decrease from
160 to 106 mA W 1 as the intensity increases from 43.5 nW to
3.46 mW at a wavelength of 650 nm. This may be attributed to the
degree of saturation of the photocurrent of the device at higher
levels of illumination. The average responsivity of our device for
the spectral rage of 400–700 nm is around 100 mA W 1.
The external quantum efficiency (EQE) decides the prob-
ability of generating a charge carrier in the photodetector upon
incident light. The external quantum efficiency can be calculated
from the responsivity for a specific wavelength and the energy of
the incident wavelength using the following relation,48
EQE = Rhn/e
here R is the responsivity, h is Planck’s constant, n is the
frequency of the light, and e is the electronic charge. We
calculated the quantum efficiency for our devices and the result
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is included in Fig. S3 (ESI†) as a function of wavelength. The
value of the quantum efficiency of our flexible device is quite
decent, around 25% for the wavelength range of 400–650 nm in
the self-biased mode.
The normalized equivalent power (NEP) is an important
figure of merit of a photodetector, which decides the minimum
incident optical power that the photodetector can differentiate
from noise. Before evaluating the noise current measurement
of the device we needed to measure the background instru-
mental noise. The instrumental noise current (i) is shown in
Fig. 5(a) (blue curve) while the device noise current is denoted by
the red color. The instrumental noise is 11 pA Hz 1 to 3.5 pA Hz 1
for the frequency range from 1 to 100 Hz. The device noise current
for the same range of frequency is 200 pA Hz 1 to 16 pA. The
instrumental noise current is much lower than the device noise,
demonstrating that the measured noise is mostly from the device.
From the measured noise current and the responsivity of the
photodetector, we have calculated the noise equivalent power
(NEP) using the following equation,48
NEP = in/R
where in is the noise current and R is the responsivity. The noise
equivalent power (NEP) for our device for the wavelength range
of 400 to 700 nm is included in Fig. 5(b) for a noise current of
15 pA Hz 1/2 at a frequency of 117 Hz. The NEP of our device is
clearly very low in the range of 10 10 W.
The response speed of the photodetector is an essential
factor for the detection of high-frequency optical signals. It
depends on how fast the charges are transported and extracted
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Fig. 4 (a) Current density (J) vs. time for the photodetector under light on and off cycles under 0 bias, at wavelengths in the range of 400–700 nm;
(b) responsivity and detectivity curves of the photodetector under different wavelengths at 0 bias; (c) current density (J) vs. time for the photodetector
under light on and off cycles under 0 bias at different light intensity illumination; and (d) photocurrent density and responsivity as a function of different
incident power values using a 650 nm wavelength light source.
towards the respective electrode after irradiation with the
optical pulse. The transient measurement for our device was
performed under 500 nm pulsed light (a pulse width of 40 ms)
from a light emitting diode (LED) in the self-powered mode.
The time calibration was performed by using a Si photodiode
having a 1 ns rise time. Fig. 5(c) shows the normalized current
as a function of time (I–t profile with time in microseconds).
The rise time of the photo-detector was calculated by the time
interval for the response to rise from 10% to 90% of its highest
value, while the fall time was calculated by the time interval for
the response to drop from 90% to 10% of its peak value. The
rise time and decay time values for our self-powered flexible
device are found to be 5.7 ms and 6.2 ms, respectively, as shown
in Fig. 5(c).
We compared the data for our flexible self-powered photo-
detector device with previously reported photo-detectors based
on inorganic halide perovskites, hybrid perovskites and other
materials; the comparison is shown in Table 1.57–70 It can be
concluded that our photo-detector has a fast response and high
detectivity better than or at least comparable to most cases, in
addition to its virtues of a self-powered mode and flexibility.
6992 | J. Mater. Chem. C, 2019, 7, 6986--6996
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Theoretically, the 3 dB cut-off frequency is calculated using
the following relation,48
f3dB E 0.443/ttr
where ttr is the transit time of the device, which is 5.7 ms for our
case. Based on the transit time the 3 dB cut off frequency can be
calculated as 0.0759 MHz. The frequency response of the device
was measured with a square wave voltage driven green LED
(l = 500 nm) and the generated photocurrent was measured
using an oscilloscope. From the amplitude of the photocurrent
recorded for different frequencies, we obtained the frequency
response, which is shown in Fig. 5(d).
The experimental 3 dB cut off frequency for our devices is
0.077 MHz, which matches well with the calculated value
(0.0759 MHz). For the real-world application of the flexible
photo-detector, it should have good stability after bending
cycles. The device performance with several bending cycles
was therefore measured as a function of the photocurrent on/
off cycles with respect to time, and the corresponding data are
included in Fig. 6(b). The process of bending of the device is
shown in Fig. 6(a) (I–IX). Interestingly the performance is stable
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Fig. 5 (a) Noise current spectra of the photodetector as well as the instrumental noise in the dark with a 50 mV bias, (b) noise equivalent power (NEP)
of the device as a function of wavelength, considering the noise current at 117 Hz frequency, (c) time transient measurement result for the photodetector,
and (d) the frequency response of the device.

Table 1 Comparison table of previously reported photo-detectors

Device Flexible Bias (V) l (nm) R (A W 1) D* (Jones) tr/tf Ref.

ITO/SnO2/CsPbI3/Au Yes 0 400–700 40.100 1012 5.7/6.2 ms This work
Au/CsPbI3/Au Yes 1 530 0.35 1010 — 68
ITO/CH3NH3PbI3/ITO Yes 3 780 0.0367 100/100 ms 60
C/TiO2/MAPbI3/spiro/Au (#) Yes 0 550 0.0169 1010 200/200 ms 59
ITO/MAPbI3/ITO Yes 1 400–760 81 1011 230/280 ms 67
Au/PDOT:PSS/MAPbI3/PCBM/Al (#) Yes 0 300–700 B100 — 4.1/3.3 ms 58
ITO/CsPbBr3/ITO Yes 10 442 0.64 — 19/24 ms 57
Carbon/TiO2/MAPbI3/CuO/Cu2O/Cu Yes 0 350–850 0.56 1013 o200/o200 ms 66
Ni/GaN(NP)/Pt Yes 0 400 0.03 1012 100/100 ms 62
ZnO/spiro-OMeTAD Yes 0 365 8  10 4 109 160/200 ms 61
ITO/ZnO/CsPbI3(NP)/P3HT/MoO3/Ag (#) No 0.5 400–700 1012 — 70
Au/CsPbI3/Au No 2 405 2.9  103 1013 50/150 ms 69
ITO/SnO2/CsPbBr3/spiro/Au (#) No 0 465 0.172 1012 140/120 ms 65
PDOT:PSS/(FASnI3)0.6(MAPbI3)0.4/C60PCB/Al (#) No 0.2 300–1000 0.4 1012 6.9/9.1 ms 64
Au/CsPbI3(NP)/Au No 3 425–655 — — 24/29 ms 63
# Full solar cell architecture.

after even 500 bending cycles as observed from the J–t profile of
Fig. 6(b).
We studied the stability of our device under an extreme case
(without any encapsulation under ambient conditions with
humidity 485%) by keeping it under constant illumination
with a solar simulator (intensity 100 mW cm 2) and measured
the photocurrent at 0 bias for half an hour. The corresponding
normalized photocurrent vs. time profile is shown in Fig. 6(c).
There is a 40% reduction in photocurrent. The reduction in the
photocurrent may be due to the halide vacancies moving to the

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Fig. 6 (a) Process followed for bending of the photo-detector over one complete cycle (I–IX), (b) J–t profile under light on and off under 0 bias for
various bending cycles, and (c) stability of the device measured as a function of time (ambient with humidity above 80%).
respective electrodes and getting accumulated at the interfaces.
This accumulation of charges creates a barrier for the photogen-
erated charges, thereby reducing the photocurrent.71–74 Clearly,
with encapsulation the device can sustained for longer periods.
We also checked the structural stability of the PVP-CsPbI3
film itself by performing XRD of the fresh sample and after
keeping the film for 15 days under ambient atmosphere. There
is no change in the XRD pattern as shown in Fig. S4 (ESI†),
which implies that there is no phase transformation from
a-CsPbI3 to d-CsPbI3.
Conclusions
In summary, we have demonstrated low-temperature film growth
and impressive stability of the a-CsPbI3 phase by a single step
solution process, using an optimized amount of wrapping PVP
polymer as the surface functionalizing agent. This low-temperature
process and high stability of the broad-band absorbing material
enabled us to fabricate a photodetector based on a heterostructure
involving this system with n-type SnO2 on a flexible ITO coated PET
substrate. This self-powered flexible photodetector indeed exhibits
a broadband detecting capability with high detectivity (1012), on/off
ratio (103), and responsivity (B100 mA W 1) over the wavelength
range of 400–700 nm. The fast response time of a few microseconds
of the device with good stability under 500 bending cycles reflects
its potential for practical use as a low-cost photodetector for
wearable devices.
Conflicts of interest
There are no conflicts to declare.
6994 | J. Mater. Chem. C, 2019, 7, 6986--6996
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Acknowledgements
Satish Ogale would like to thank DST Nanomission Thematic
unit for funding support, DST-CERI, DST-UKERI, and GCRF-
SUNRISE for funding. We would like to thank Dr Angshuman
Nag for providing the photoluminescence facility.
Notes and references
1 Y.-C. Chen, Y.-J. Lu, C.-N. Lin, Y.-Z. Tian, C.-J. Gao, L. Dong
and C.-X. Shan, J. Mater. Chem. C, 2018, 6, 5727–5732.
2 Y. Li, Z. F. Shi, X. J. Li and C. X. Shan, Chin. Phys. B, 2019,
28, 017803.
3 J. Zheng, R. A. Barton and D. Englund, ACS Photonics, 2014,
1, 768–774.
4 N. Mondal, A. De and A. Samanta, ACS Energy Lett., 2018, 32–39.
5 J. Song, L. Xu, J. Li, J. Xue, Y. Dong, X. Li and H. Zeng,
Adv. Mater., 2016, 28, 4861–4869.
6 F. Teng, K. Hu, W. Ouyang and X. Fang, Adv. Mater., 2018,
30, 1706262.
7 D. Liu and T. L. Kelly, Nat. Photonics, 2014, 8, 133–138.
8 U. Bansode, R. Naphade, O. Game, S. Agarkar and S. Ogale,
J. Phys. Chem. C, 2015, 119, 9177–9185.
9 Z. Xiao, L. Zhao, N. L. Tran, Y. L. Lin, S. H. Silver, R. A.
Kerner, N. Yao, A. Kahn, G. D. Scholes and B. P. Rand, Nano
Lett., 2017, 17, 6863–6869.
10 S. D. Stranks, G. E. Eperon, G. Grancini, C. Menelaou,
M. J. P. Alcocer, T. Leijtens, L. M. Herz, A. Petrozza and
H. J. Snaith, Science, 2013, 342, 341–344.
11 S. De Wolf, J. Holovsky, S. J. Moon, P. Löper, B. Niesen,
M. Ledinsky, F. J. Haug, J. H. Yum and C. Ballif, J. Phys.
Chem. Lett., 2014, 5, 1035–1039.
This journal is © The Royal Society of Chemistry 2019

Paper
12 A. Kumar, A. K. Mishra, U. Bansode, S. Ogale and
A. Rahman, Nanotechnology, 2018, 29, 405701.
13 I. Deretzis, E. Smecca, G. Mannino, A. La Magna,
T. Miyasaka and A. Alberti, J. Phys. Chem. Lett., 2018, 9,
3000–3007.
14 D. J. Slotcavage, H. I. Karunadasa and M. D. McGehee, ACS
Energy Lett., 2016, 1, 1199–1205.
15 W. Ahmad, J. Khan, G. Niu and J. Tang, Sol. RRL, 2017,
1, 1700048.
16 W. Du, S. Zhang, J. Shi, J. Chen, Z. Wu, Y. Mi, Z. Liu, Y. Li,
Published on 07 May 2019. Downloaded by KEAN UNIVERSITY on 7/18/2019 8:46:08 AM.
X. Sui, R. Wang, X. Qiu, T. Wu, Y. Xiao, Q. Zhang and X. Liu,
ACS Photonics, 2018, 5, 2051–2059.
17 I. Dursun, Y. Zheng, T. Guo, M. De Bastiani, B. Turedi,
L. Sinatra, M. A. Haque, B. Sun, A. A. Zhumekenov,
M. I. Saidaminov, F. P. Garcı́a De Arquer, E. H. Sargent,
T. Wu, Y. N. Gartstein, O. M. Bakr, O. F. Mohammed and
A. V. Malko, ACS Energy Lett., 2018, 3, 1492–1498.
18 M. I. Saidaminov, M. A. Haque, J. Almutlaq, S. Sarmah,
X. H. Miao, R. Begum, A. A. Zhumekenov, I. Dursun, N. Cho,
B. Murali, O. F. Mohammed, T. Wu and O. M. Bakr, Adv.
Opt. Mater., 2017, 5(2), 1600704.
19 G. E. Eperon, G. M. Paternò, R. J. Sutton, A. Zampetti,
A. A. Haghighirad, F. Cacialli and H. J. Snaith, J. Mater.
Chem. A, 2015, 3, 19688–19695.
20 Y. Hu, F. Bai, X. Liu, Q. Ji, X. Miao, T. Qiu and S. Zhang,
ACS Energy Lett., 2017, 2, 2219–2227.
21 W. Cai, Z. Chen, Z. Li, L. Yan, D. Zhang, L. Liu, Q. Xu, Y. Ma,
F. Huang, H.-L. Yip and Y. Cao, ACS Appl. Mater. Interfaces,
2018, 10, 42564–42572.
22 P. Wang, X. Zhang, Y. Zhou, Q. Jiang, Q. Ye, Z. Chu, X. Li,
X. Yang, Z. Yin and J. You, Nat. Commun., 2018, 9, 2225.
23 Y. Wang, T. Zhang, M. Kan, Y. Li, T. Wang and Y. Zhao,
Joule, 2018, 2, 2065–2075.
24 B. Li, Y. Zhang, L. Fu, T. Yu, S. Zhou, L. Zhang and L. Yin,
Nat. Commun., 2018, 9, 1076.
25 S. Xiang, W. Li, Y. Wei, J. Liu, H. Liu, L. Zhu and H. Chen,
Nanoscale, 2018, 10, 9996–10004.
26 A. K. Jena, A. Kulkarni, Y. Sanehira, M. Ikegami and
T. Miyasaka, Chem. Mater., 2018, 30, 6668–6674.
27 C. F. J. Lau, X. Deng, J. Zheng, J. Kim, Z. Zhang, M. Zhang,
J. Bing, B. Wilkinson, L. Hu, R. Patterson, S. Huang and
A. Ho-Baillie, J. Mater. Chem. A, 2018, 6, 5580–5586.
28 T. Zhang, M. I. Dar, G. Li, F. Xu, N. Guo, M. Grätzel and
Y. Zhao, Sci. Adv., 2017, 3, e1700841.
29 Q. Wang, X. Zheng, Y. Deng, J. Zhao, Z. Chen and J. Huang,
Joule, 2017, 1, 371–382.
30 Z. Tang, S. Uchida, T. Bessho, T. Kinoshita, H. Wang,
F. Awai, R. Jono, M. M. Maitani, J. Nakazaki, T. Kubo and
H. Segawa, Nano Energy, 2018, 45, 184–192.
31 Q. Ma, S. Huang, X. Wen, M. A. Green and A. W. Y. Ho-
Baillie, Adv. Energy Mater., 2016, 6, 1502202.
32 C. Liu, W. Li, C. Zhang, Y. Ma, J. Fan and Y. Mai, J. Am.
Chem. Soc., 2018, 140, 3825–3828.
33 C. F. J. Lau, M. Zhang, X. Deng, J. Zheng, J. Bing, Q. Ma,
J. Kim, L. Hu, M. A. Green, S. Huang and A. Ho-Baillie,
ACS Energy Lett., 2017, 2, 2319–2325.
This journal is © The Royal Society of Chemistry 2019
View Article Online
Journal of Materials Chemistry C
34 R. Begum, M. R. Parida, A. L. Abdelhady, B. Murali,
N. M. Alyami, G. H. Ahmed, M. N. Hedhili, O. M. Bakr
and O. F. Mohammed, J. Am. Chem. Soc., 2017, 139,
731–737.
35 Y. Jiang, J. Yuan, Y. Ni, J. Yang, Y. Wang, T. Jiu, M. Yuan and
J. Chen, Joule, 2018, 2, 1356–1368.
36 E. M. Sanehira, A. R. Marshall, J. A. Christians, S. P. Harvey,
P. N. Ciesielski, L. M. Wheeler, P. Schulz, L. Y. Lin,
M. C. Beard and J. M. Luther, Sci. Adv., 2017, 3, eaao4204.
37 A. Swarnkar, A. R. Marshall, E. M. Sanehira, B. D.
Chernomordik, D. T. Moore, J. A. Christians,
T. Chakrabarti and J. M. Luther, Science, 2016, 354, 92–95.
38 K. P. Mubiayi, N. Moloto and M. J. Moloto, CrystEngComm,
2018, 20, 5275–5280.
39 B. Zhao, S.-F. Jin, S. Huang, N. Liu, J.-Y. Ma, D.-J. Xue,
Q. Han, J. Ding, Q.-Q. Ge, Y. Feng and J.-S. Hu, J. Am. Chem.
Soc., 2018, 140, 11716–11725.
40 Y. Fu, M. T. Rea, J. Chen, D. J. Morrow, M. P. Hautzinger,
Y. Zhao, D. Pan, L. H. Manger, J. C. Wright, R. H. Goldsmith
and S. Jin, Chem. Mater., 2017, 29, 8385–8394.
41 Y. Wang, T. Zhang, M. Kan and Y. Zhao, J. Am. Chem. Soc.,
2018, 140, 12345–12348.
42 A. Marronnier, G. Roma, S. Boyer-Richard, L. Pedesseau,
J.-M. Jancu, Y. Bonnassieux, C. Katan, C. C. Stoumpos, M. G.
Kanatzidis and J. Even, ACS Nano, 2018, 12, 3477–3486.
43 R. J. Sutton, M. R. Filip, A. A. Haghighirad, N. Sakai,
B. Wenger, F. Giustino and H. J. Snaith, ACS Energy Lett.,
2018, 3, 1787–1794.
44 H. Wang, X. Qiao, J. Chen, X. Wang and S. Ding, Mater.
Chem. Phys., 2005, 94, 449–453.
45 M. Kim, S. G. Motti, R. Sorrentino and A. Petrozza, Energy
Environ. Sci., 2018, 11, 2609–2619.
46 D. Jousse, C. Constantino and I. Chambouleyron, J. Appl.
Phys., 1983, 54, 431–434.
47 Y. Huang, W. J. Yin and Y. He, J. Phys. Chem. C, 2018, 122,
1345–1350.
48 J. M. Liu, Photonic devices, 2005, 935–944.
49 L. Dou, Y. M. Yang, J. You, Z. Hong, W. H. Chang, G. Li and
Y. Yang, Nat. Commun., 2014, 5, 5404.
50 G. Konstantatos, J. Clifford, L. Levina and E. H. Sargent, Nat.
Photonics, 2007, 1, 531–534.
51 C. Bao, Z. Chen, Y. Fang, H. Wei, Y. Deng, X. Xiao, L. Li and
J. Huang, Adv. Mater., 2017, 29, 1703209.
52 D. Y. Guo, C. X. Shan, S. N. Qu and D. Z. Shen, Sci. Rep.,
2014, 4, 7469.
53 D.-H. Kwak, D.-H. Lim, H.-S. Ra, P. Ramasamy and J.-S. Lee,
RSC Adv., 2016, 6, 65252–65256.
54 Y. Wang, Y. Zhang, Y. Lu, W. Xu, H. Mu, C. Chen, H. Qiao,
J. Song, S. Li, B. Sun, Y.-B. Cheng and Q. Bao, Adv. Opt.
Mater., 2015, 3, 1389–1396.
55 I. Ka, L. F. Gerlein, R. Nechache and S. G. Cloutier, Sci. Rep.,
2017, 7, 45543.
56 C. Lan, R. Dong, Z. Zhou, L. Shu, D. Li, S. Yip and J. C. Ho,
Adv. Mater., 2017, 29, 1702759.
57 J. Song, L. Xu, J. Li, J. Xue, Y. Dong, X. Li and H. Zeng,
Adv. Mater., 2016, 28, 4861–4869.
J. Mater. Chem. C, 2019, 7, 6986--6996 | 6995

Journal of Materials Chemistry C
58 C. Bao, W. Zhu, J. Yang, F. Li, S. Gu, Y. Wang, T. Yu, J. Zhu,
Y. Zhou and Z. Zou, ACS Appl. Mater. Interfaces, 2016, 8,
23868–23875.
59 H. Sun, T. Lei, W. Tian, F. Cao, J. Xiong and L. Li, Small,
2017, 13, 1701042.
60 X. Hu, X. Zhang, L. Liang, J. Bao, S. Li, W. Yang and Y. Xie,
Adv. Funct. Mater., 2014, 24, 7373–7380.
61 Y. Shen, X. Yan, H. Si, P. Lin, Y. Liu, Y. Sun and Y. Zhang,
ACS Appl. Mater. Interfaces, 2016, 8, 6137–6143.
62 M. Peng, Y. Liu, A. Yu, Y. Zhang, C. Liu, J. Liu, W. Wu,
Published on 07 May 2019. Downloaded by KEAN UNIVERSITY on 7/18/2019 8:46:08 AM.
K. Zhang, X. Shi, J. Kou, J. Zhai and Z. L. Wang, ACS Nano,
2016, 10, 1572–1579.
63 P. Ramasamy, D. H. Lim, B. Kim, S. H. Lee, M. S. Lee and
J. S. Lee, Chem. Commun., 2016, 52, 2067–2070.
64 W. Wang, D. Zhao, F. Zhang, L. Li, M. Du, C. Wang,
Y. Yu, Q. Huang, M. Zhang, L. Li, J. Miao, Z. Lou, G. Shen,
Y. Fang and Y. Yan, Adv. Funct. Mater., 2017, 27(42),
1703953.
65 H. Zhou, J. Zeng, Z. Song, C. R. Grice, C. Chen, Z. Song,
D. Zhao, H. Wang and Y. Yan, J. Phys. Chem. Lett., 2018, 9,
2043–2048.
6996 | J. Mater. Chem. C, 2019, 7, 6986--6996
View publication stats
View Article Online
Paper
66 H. Sun, W. Tian, F. Cao, J. Xiong and L. Li, Adv. Mater., 2018,
30, 1706986.
67 W. Hu, W. Huang, S. Yang, X. Wang, Z. Jiang, X. Zhu,
H. Zhou, H. Liu, Q. Zhang, X. Zhuang, J. Yang, D. H. Kim
and A. Pan, Adv. Mater., 2017, 29, 1703256.
68 Y. Zhou, J. Luo, Y. Zhao, C. Ge, C. Wang, L. Gao, C. Zhang,
M. Hu, G. Niu and J. Tang, Adv. Opt. Mater., 2018, 6, 1800679.
69 T. Yang, Y. Zheng, Z. Du, W. Liu, Z. Yang, F. Gao, L. Wang,
K.-C. Chou, X. Hou and W. Yang, ACS Nano, 2018, 12,
1611–1617.
70 K. M. Sim, A. Swarnkar, A. Nag and D. S. Chung, Laser
Photonics Rev., 2018, 12, 1700209.
71 W. Zhou, Y. Zhao, X. Zhou, R. Fu, Q. Li, Y. Zhao, K. Liu,
D. Yu and Q. Zhao, J. Phys. Chem. Lett., 2017, 8, 4122–4128.
72 P. Vashishtha and J. E. Halpert, Chem. Mater., 2017, 29,
5965–5973.
73 Y. Yuan and J. Huang, Acc. Chem. Res., 2016, 49, 286–293.
74 W. Nie, J. C. Blancon, A. J. Neukirch, K. Appavoo, H. Tsai,
M. Chhowalla, M. A. Alam, M. Y. Sfeir, C. Katan, J. Even,
S. Tretiak, J. J. Crochet, G. Gupta and A. D. Mohite,
Nat. Commun., 2016, 7, 11574.
This journal is © The Royal Society of Chemistry 2019