Chapter 4

Photoactive Piezoelectric Energy Harvester and Photodetector based on

Organo-Lead Halide Perovskite and PVDF Film

88
4.1 Introduction

The requirements of self-powered portable electronic system eager the development of

suitable materials for efficient and hybridized renewable energy harvesting. For example,

solar, thermal, mechanical, geothermal, vibration, sonic wave and wind are the various type

of renewable energy available in our surrounding, among them solar and mechanical are the

most promising and valuable because of its greater accessibility and hybridizing possibilities.

However, due to the drastically different physical principles, the existing approaches

developed so far are mostly designed to uniquely harvest the mechanical or the solar energy.

In general, organo-lead halide perovskites are mostly used materials in light energy

harvesting application due to their excellent optical and electronic properties that contribute

to high efficiency in solar energy conversion systems.1-4 In particular, photon-absorbing

perovskite structured methylammonium lead halides (CH3NH3PbX3, X= Cl, Br, I) have

attracted much attention in recent years in the arena of photovoltaic related research.5-7 Due

to direct band gap semiconducting properties they are also good absorbers of a large spectrum

of solar energy and also possess large absorption coefficient and high carrier mobility.6,7

Besides, photovoltaic research, perovskite based photodetectors have also gained enormous

interest in recent years.8 However, stability of these materials is of extensive anxiety for the

technology of solar cells and photodetectors where moisture is conceived to be the main

degradation source on account of their intrinsic hydrophilic property.9 Hence, significant

efforts have been devoted toward investigations on stability and encapsulation of perovskite

materials for improvement of the lifecycle of the devices.10,11 An interesting functionality

may be added if the encapsulation layer which is useful for protecting the perovskite

materials can be used for harvesting mechanical energies. Currently, piezoelectric

nanogenerators have been developed to convert mechanical energy from irregular mechanical

vibrations to electricity. It can be fabricated using flexible polymer materials since inorganic

89
piezoelectric materials are limited due to their fragile nature. Thus a hybrid energy harvester

may be fabricated to simultaneously/separately harvest multimode energies, whichever is

available if photoactive component is being introduced in piezoelectric polymers.

It should also be mentioned that piezoelectric materials are also dielectric thus the output

current generated from piezoelectric nanogenerator is generally quite low. Therefore

improvement of current from piezoelectric nanogenerator also becomes a challenging task.

Generally, ceramic piezoelectric materials show superior mechanical energy harvesting

properties but they are limited by their rigid and brittle nature.12 In contrast, piezoelectric

polymers are flexible, lightweight non-toxic and easy to process. It has been found that PVDF

is one of the best known piezoelectric polymer that has tremendous potential to use in

sensors, actuators, biomedical and mechanical energy-harvesting applications owing to its

soft, biocompatible and light weight nature. This is a semi-crystalline polymer that exhibit at

least four distinct crystalline phases viz., -, -, - and -phase.13,14 Among them, the polar β

(TTTT conformation) and semi-polar γ (T3G+T3G- conformation) crystalline phases are more

attractive due to their superior piezo-, pyro- and ferroelectric properties whereas α (TGTG

conformation) phase is electrically nonactive. The alignment of all the –CH2/-CF2 dipoles in

the direction normal to the chain axis of PVDF, makes the -phase highly polar

conformation.13 However, from the energy harvesting point of view -phase is most desirable

due to the highest dipolar moment per unit cell compared to -phase.13,15 The -phase can be

obtained by preferentially orient the -CH2/-CF2 dipoles of PVDF.16 Among various methods

available to achieve  phase (e.g., mechanical stretching, electric poling, annealing, melt

under high pressure, addition of hydrated salts and electrospinning) incorporation of external

assisting agents in PVDF matrix to prepare a composite structure is most desirable to avoid

undesired structural deformations and energy consumption.17,18 Recent study indicates that

higher -phase content, larger charge collecting area and improved strain effect is responsible

90
to achieve enhanced piezoelectric response and sensing in porous PVDF.19,20 Thus several

approaches have been undertaken to create porous structure in PVDF films.19,20 Noteworthy

to mention that the efficiency enhancement of solar cell is also feasible by incorporation of

ferroelectric constituent. For instances, the internal electric field of -phase of ferroelectric

PVDF is thus useful to reduce electron hole recombination by dissociating single electrons

holes and charge transfer excitons that improve the device performance.21,22

A single device with multifunctional application has been a new trend in energy

technologies.23-26 Thus, induction of polar β-phase in PVDF and optical absorption property

of MAPI are both of great importance to make a composite that is suitable for mechanical

energy harvester as well as photodetector and their hybridization. The optical absorption

property may also be responsible for improvement of the output current of piezoelectric

nanogenerator. To the best of our knowledge no attempt has been undertaken for induction of

-phase and porous structure in PVDF by incorporation of MAPI to make it suitable for

mechanical energy harvesting, photodetector application and hybridize photoactive

piezoelectric energy harvester.

In this work, we have synthesized methylammonium lead iodide (MAPI) via simple co-

precipitation method and prepared MAPI incorporated -phase containing PVDF composite

film by solution casting method in ambient environment. It seems that MAPI is not only

inducing -phase but also causing porous structure in PVDF. On the other hand, PVDF

encapsulation prevents the degradation of MAPI from moisture and oxygen. We report the

hybrid photoactive mechanical energy harvester made with MAPI embedded -phase

comprising porous polyvinylidene fluoride (PVDF) composite (MPC) films. It is also capable

of detecting visible light which leads to significant change of output voltage (∼42 %) and

current (∼39 %) that pave the way to work as self-powered photodetector.

91
4.2 Experimental Section

PVDF pellets (Mw ≈ 275 000 gm/mol, Sigma-Aldrich, USA), DMF (Merck Chemicals,

India), polydimethylsiloxane (PDMS) (Sylgard184, Dow Corning Corp., USA), indium tin

oxide (ITO) coated glass and PET substrates (Sigma-Aldrich), methylamine (CH3NH2)

(LOBA Chemie), hydroiodic acid (HI) (Otto Chemie), lead (II) iodide (PbI2) (Otto Chemie),

γ-butyrolactone (LOBA Chemie).

4.2.1 Methylammonium lead iodide Synthesis

Preparation of methylammonium iodide (CH3NH3I) is the first step towards synthesis of

methylammonium lead iodide (CH3NH3PbI3). To synthesize CH3NH3I, equimolar solution of

CH3NH2 and HI were mixed in ice bath and kept on stirring for 2 hours. Then the resulting

solution was heated at 60 ˚C for 1 hour in nitrogen atmosphere and then precipitate was

recovered. This precipitate was then washed with diethyl ether and filtered to get CH3NH3I

powder. After that it was vacuum dried for further use.

Equimolar amount of as synthesized CH3NH3I and PbI2 was dissolved in γ-

butyrolactone and stirred at 60˚ C in nitrogen atmosphere. Finally, shiny black powder of

(CH3NH3PbI3) (digital photograph is shown in supporting information, Fig. 4.1a) was

recovered as precipitate which was vacuum dried and stored.

4.2.2 MPC film preparation

12 wt% (w/v) PVDF pellets was dissolved in DMF to prepare the stock solution. The stock

solutions were blended separately with 0.025, 1, 3, 5, 7, 10 and 12 wt% (w/v) of MAPI then

vigorously stirred at room temperature for 24 h (one resulting solution is shown in Fig. 4.1b).

PVDF-MAPI solutions were then casted on clean glass slides and subsequently dried at 90 oC

for 6 h. Finally as-cast films (thickness ~20 µm) were peeled off from glass slides and named

as PVDF (with no additives), and MPC#, # represents concentration of MAPI (Fig. 4.1c).

92
 (a) (b)

(c)
PVDF MPC(0.025) MPC(1) MPC(10)

Fig. 4.1 Photographic image of (a) synthesized MAPI powder. (b) Solution of MPC(1) in

PVDF. (c) Resultant PVDF, MPC(0.025), MPC(1) and MPC(10) films. Scale bar is of 0.5

cm.

4.2.3 Characterization

Field emission scanning electron microscopy (FESEM, FEI, INSPECT F50) images were

recorded to investigate the detail surface morphological characteristics of the as-cast MPC.

MPC were characterized using fourier transform infrared spectroscopy (FT-IR, Bruker,

Tensor II with ATR attachment (Pike MIRacle)). Thin film of MAPI was deposited on glass

substrate in order to perform UV-vis spectroscopy using Optizen POP (South Korea) UV-

Vis-NIR spectrophotometer. To investigate the crystallographic structure of the MAPI and

MPC films, X-ray diffraction pattern (XRD, Bruker, D8 Advance) was recorded. Open-

circuit voltage was recorded by connecting the piezoelectric energy harvester (PEH) with a

national instrument (NI) data acquisition (DAQ) device (NI, USB 6000) using a sampling

rate of 1000 samples per second, interfaced with a computer with a standalone program made

by using LabVIEW software and current measurements were carried out with Keithley 6485

picoammeter. The current-voltage (I-V) characteristics measurements were carried out using

Keithley 2602B dual channel source meter. The photocurrent measurement with different

93
color LEDs were performed with Nvis 105CT digital storage oscilloscope. Light intensities

of the LEDs were measured with calibrated optical power meter.

4.3 Results and Discussion

4.3.1 Characterization of MAPI

X-ray diffraction pattern (Fig. 4.2a) of synthesized MAPI confirms the formation of pure

perovskite phase.27

(a) (b)

(c) (d)

50 µm

Fig. 4.2 (a) XRD spectra, (b) UV-vis absorption spectra, (c) Tauc plot for determination of

the direct band gap energy and (d) FE-SEM micrograph with particle size distribution plot in

the inset of the as prepared MAPI.

The UV-vis absorption spectra of MAPI (Fig. 4.2b) shows a broad absorption ranging from

400 to 800 nm. The optical band gap of the MAPI is determined from the Tauc plot as

depicted in Fig. 4.2c. The band gap energy (Eg) of MAPI was determined from a tauc plot

94
using (hν)2 versus energy relation. The relation between the absorption coefficient (α) and

the photon energy (hν) is, (hν)1/n = A(hν- Eg), where, A = constant, Eg = band gap energy

and the value of n for direct allowed transition is 1/2. (hν)1/n versus hν was plotted in Fig.

4.2c and the band gap value were obtained by extrapolating the steepest portion of the graph

on the hν axis. The direct band gap energy of the MAPI was found to be 1.51 eV. This result

is in good agreement with previously reported values.28 FE-SEM image and particle size

distribution curve shown in Fig. 4.2d illustrates that average diameter of particle around

16±4.2 μm are formed.

(a) (b)

Fig. 4.3 (a) Static FT-IR spectra of PVDF and MPC films in a range of 1600–550 cm-1. (b)

Dependency of electroactive phases of MPC films as a function of MAPI content. Inset

presents the FT-IR spectra of PVDF and MPC films in a range of 3070–2935 cm-1.

4.3.2 Characterization of MPC films

FT-IR spectra of neat PVDF and MPC films are shown in Fig. 4.3a. The neat PVDF shows

predominantly -phase as evidenced from the vibrational bands at 1214, 1150, 976, 856, 796,

764 and 613 cm-1. In contrast, MPC films are exhibiting new prominent bands appeared at

1275 and 1234 cm-1 that correspond to the - and  phases respectively.29-31 Moreover the

peak at 841 cm-1 is a dual signature for the presence of - and  phases. 29,30 Noteworthy that

95
nucleation of the electroactive - and -phases and reduction of the -crystalline growth takes

place even with a little amount of (0.025 wt%) MAPI. The -phase content decreases with an

increase in MAPI concentration and completely disappeared at 1 wt%. The intensity of 1275

and 1234 cm-1 band increases with increment of MAPI content and starts to reduce after 10

wt%. This result clearly revealed that the MAPI is playing a significant role in crystalline

phase transformation and improvement of electroative β and γ-phase content in PVDF. The

electroactive phase (FEA) content in MPC films as a function of MAPI concentration is

illustrated in Fig. 4.3b. It increases with MAPI content, saturates at 10 wt% and then

gradually starts to decrease. Due to very close value of electroactive phase content in

MPC(3), MPC(5), MPC(7) and MPC(10), mainly we choose two low (MPC(0.025), MPC(1))

and one high MAPI containing film (MPC(10)) for further characterization as well as utilized

for device fabrication and its applications. As the 841 cm-1 band is a dual signature of - and

- phase, thus the relative proportion of electroactive - and - phase phases in the MPC films

is given by,

𝐼𝐸𝐴
𝐹𝐸𝐴 = × 100 % (4.1)
𝐾
(𝐾841 ) 𝐼764 + 𝐼𝐸𝐴
764

where, IEA and I764 are the absorbance intensities at 841 and 764 cm-1 respectively, K841 (7.7

× 104 cm2 mol−1) and K764 (=6.1 × 104 cm2 mol−1) are the absorption coefficients at the

respective wave numbers.32

It is already been reported that the vibrational bands at 1234 and 1275 cm-1 are unique. Thus

to quantify the relative proportion of electroactive - and -phases individually the following

equations are used.

𝐴𝛽
𝐹 = 𝐹𝐸𝐴 × × 100 % (4.2)
𝐴 + 𝐴

𝐴
𝐹 = 𝐹𝐸𝐴 × × 100 % (4.3)
𝐴 + 𝐴

96
where Aβ and A are the absorbance intensities at 1275 and 1234 cm−1 band respectively. The

resultant content of electroactive phase (FEA) and relative proportion of - (F), and - (F)

phases are individually estimated in selected MPC films and summarized in Table 4.1.

Table 4.1 Comparison of different phase content in MPC films

Film Electroctive Phase -phase (F%) -phase (F%)

MPC(1) 90.2 40 50.2

MPC(10) 90.6 40.6 50

For instance, MPC(10) film contains higher yield of the electroactive phase (~ 91 %) with 41

% and 50 % of - and -phase respectively which is expected to be superior for designing

piezoelectric based sensors and energy harvesters.

FTIR spectra of the MPC films are also shown in the 3070–2935 cm-1 region (inset of Fig.

4.3b) for studying the electroactive phase formations by interfacial interaction of the -CH2

dipoles with MAPI. This region is extremely useful to check the interfacial interactions

between the external filler i.e., MAPI and the CH2 dipoles of PVDF because it is attributed to

the -CH2 asymmetric (νas) and symmetric (νs) stretching vibrational bands and they are not

coupled with any other vibrational modes.32 Thus, shifting of these bands are expected if any

disruption of the vibrations appeared. Likewise, the positions of νas and νs vibrational bands

of -CH2 are shifted toward lower energies (ῡ) in MPC films in comparison to PVDF film (ῡo)

as shown in inset of Fig. 4.3b, manifesting the interfacial interaction between MAPI and

PVDF.

It is due to fact that the interfacial interactions increase the effective mass of the -CH2 dipoles

which results a decrease in the vibrational frequency of the CH2 stretching vibration. This

97
interaction act as a damping source and the angular frequency (ωint) of CH2 stretching

vibration is related to the damping constant rdc as

ω2 = ωo2- rdc2 (4.4)

where ωo is angular frequency of CH2 stretching vibration for damping free oscillation

occurring in neat PVDF.

(a) (b)

Fig. 4.4 (a) Variation of damping co-efficient (rdc) with the loading of MAPI within the

PVDF matrix. (b) FT-IR spectra of the composite films showing the stability of the polar

phases after four months.

Thus, in terms of wavenumber,

rdc = 2πc (𝜈̅ o2 ̶ 𝜈̅ ) 1/2 (4.5)

The change of rdc with different MAPI loading is evident from Fig. 4.4a. It exhibits that rdc

increases with increasing MAPI content. It is also notable that the FEA (shown in Table 4.1)

and rdc as a function of MAPI content are analogous, suggesting a direct relationship between

the electroactive phase formation in PVDF due to interfacial interaction of the CH2 dipoles

and MAPI.12,13,17,19,32 In order to check the stability of -phase in the MPC composite film,

FT-IR measurement were carried out after four months where they kept in ambient condition

(Fig. 4.4b). It is found that -phase content is remaining the same that indicates that

composite films are quite stable.

98
 (a)

(b)

MAPI

PVDF
chain

Fig. 4.5 (a) The crystal structure of MAPI perovskite. (b) A schematic showing the proposed

mechanism for the formation of electroactive phase in the MPC film.

Therefore, depending on the experimental results and the literature review, a schematic of the

interaction between the MAPI and PVDF is presented. In organic-inorganic hybrid lead

iodide perovskite compound, the monocationic charge on methylammonium (CH3NH3+) is

localized on the three ammonium hydrogen atoms because of much greater electronegative

characteristic of the nitrogen atom in the cages constituted by inorganic PbI3− framework

(Fig. 4.5a). The electronegative iodine atoms of the PbI3− frame work resulting the negative

99
charge density that in turn electrostatically interact with -CH2 dipoles, which facilitates the

nucleation of electroactive phases as shown in the schematic (Fig. 4.5b). It is proposed that

the interaction between negative charge (PbI3- anions) and –CH2 dipoles is responsible for

the induction of -phase which is supported by the shifting of -CH2 stretching in the 3070–

2935 cm-1 region. In the interface (where dielectric interface layer was formed) the

electrostatic interaction takes place that initiate the preferable nucleation of electroactive

phase, successively it leads to the presence of electroactive phase throughout the entire

composite film. Thus the resulting film possesses the piezoelectric properties.30

XRD pattern illustrated in Fig. 4.6a is also employed to investigate the crystalline phases of

PVDF. The diffraction peaks at 17.6° (100), 18.2° (202), 19.7° (110), 27.4° (111), 35.8°

(200), and 38.7° (002) appeared in neat PVDF films are the characteristic for α-crystalline

phase.33 In contrast, the α-characteristic peaks are decreased in the MPC films, whereas few

new peaks (i.e., at 19.2°, 20.8°) are appeared as clearly ascribed from the XRD pattern of

MPC(0.025). The diffraction peaks at 19.2° (002) and 20.8° (110/200) are attributing the

presence of the γ- and -phase respectively.32,33 In the MPC(1) film, the β-phase content

became more dominant as deduced from the intense diffraction peak at 20.8°. Furthermore,

the corresponding diffraction peaks of MAPI are also found in MPC(1) film that ensures the

stability of MAPI within the PVDF matrix. In case of MPC(10) film due to the higher

concentration of MAPI in PVDF, the -crystalline peak is suppressed and the MAPI

associated diffraction pattern are dominant. In other words, the characteristics diffraction

peaks of MAPI are indicating the protection of the perovskite material from degradation that

might be mainly due to the interfacial interaction and well encapsulation in PVDF matrix.

The surface morphology of the PVDF, MPC(0.025), MPC(1) and MPC(10) films are

illustrated in Fig. 4.6b-e respectively. The PVDF film shows predominant -phase, evidenced

100
from -spherulitic fibril growth (Fig. 4.6b), which is consistent with the FT-IR and XRD

results.

(a) (b)

-spherulitic growth

3 µm

(c) (d)

Tiny spots Pores

5 µm 5 µm

(e) Fig. 4.6 (a) XRD pattern for PVDF and

MPC films. Surface morphology of (b)

PVDF (c) MPC(0.025) (d) MPC(1) and

distribution plot with an average pore

diameter of 540 nm in MPC(1) film is

These -spherulitic features are hindered when the electroactive γ and β-phase start to grow

upon inclusion of MAPI filler as shown in Fig. 4.6c-e. The surface morphology of
101
MPC(0.025) film is composed with tiny spots (Fig. 4.6c), however any open pores are not

formed. Normally in presence of moisture, MAPI decomposes to CH 3NH3I and PbI2 as

shown in equation (4.6) and CH3NH3I further decompose to methylamine and hydroiodic

acid (equation (4.7)).34

CH3NH3PbI3 (s)  CH3NH3I (g) + PbI2 (s) (4.6)

CH3NH3I (g)  CH3NH2 (g) + HI (g) (4.7)

Here in PVDF solution due to the presence of DMF, dissociation rate of MAPI increases

compared to natural degradation. Thus in case of MPC(0.025) the major portion of MAPI

may dissociate to form CH3NH2 and HI gases. But due to small amount of MAPI the

effective pore formation are not taking place on the film surface. Rather it leads to some tiny

spots on the surface of MPC(0.025). In contrast, homogeneous pores are formed on the

surface of MPC(1) (Fig. 4.6d).

10 µm

Fig. 4.7 Cross sectional view of MPC(1) film with a porous structure.

The enlarged cross-sectional view of MPC(1) film (Fig. 4.7) shows that prolate spheroid-

shaped voids are separated by insulating dielectric polymer layer which is the characteristic

feature of a ferroelectretic material.35 A pore diameter distribution plot is illustrated in the

102
inset of Fig. 4.6d, where the average pore diameter is found to be ~ 540 nm. However, the

MPC(10) film exhibits an inhomogeneous distribution of pores (Fig. 4.6e) throughout the

surface due to higher content of MAPI filler. These types of electret structure are very

common for mechanical energy harvesting applications.36

4.3.3 Mechanical energy harvesting performance

To investigate the piezoelectric response with energy harvesting ability of PVDF,

MPC(0.025), MPC(1) and MPC(10) films, PEHs are fabricated (schematics shown in Fig.

4.8a) and named as ref PEH, PEH(0.025), PEH(1), and PEH(10), respectively. Without any

electrical poling treatment, mechanical energy harvesting properties of the PEHs were

measured, where mechanical energy was applied by repeated human finger imparting (under

2 kPa pressure amplitude).37

Casting of MPC
Glass Fabricated PEH
solution Electrode attachment

Glass MPC Electrode

(b) (c)

Fig. 4.8 (a) Schematic of PEH fabrication and operation. Generation of (b) open circuit

voltage and (c) short circuit current from PEHs during human finger touch and release

process.

103
Since MPC films are composed of polar - and γ-phases, they are exhibiting superior

piezoelectric properties than PVDF (Fig. 4.8b and 4.8c). The open circuit voltage is improved

from 0.2 V to 1.5 V when the MAPI loading increases from 0 to 1 wt% in PVDF matrix. As

the FEA value of MPC(10) is comparable with MPC(1) (Fig. 4.3b), thus PEH(10) shows

comparable output performance to the PEH(1). The maximum open circuit voltage and short

circuit current arrived up to 1.8 V (Fig. 4.8b) and 37.5 nA (Fig. 4.8c) respectively in

PEH(10). The enhanced piezoelectric response of electroactive phase dominant films are due

to the overall charge distributed across the entire crystal structure constituting MAPI and the

polar electroactive part of PVDF. Throughout the human finger imparting process PEH’s

went through a strain that made a deformation in its crystal structure to a stable one or vice

versa, heading to the introduction of a piezoelectric potential across the surface of the film.

Then charge induces on upper and lower electrodes due to this piezoelectric potential that

contributes to the ultimate electrical output signal. Open circuit voltage and short circuit

current with positive (imparting of human finger) and negative (releasing of human finger)

amplitudes are produced because of this electrical potential difference appeared across the

two electrodes of the PEH’s. Hence, this composite material can be used to harvest

biomechanical energy from human body, relevant for touchable sensors such as footpaths,

shoes, vehicles etc. In addition, the MPC composite films allow for a new platform for

harvesting vibrationally bared energies accessible in surroundings.

To analyze the output power of PEH(10), the output voltage signals were recorded as a

function of external load resistances (RL) ranging from 30 kΩ to 10 MΩ (Fig. 4.9a) (as shown

by circuit diagram in the inset). The output voltage signals (VL) across the load resistances

gradually improved with the increasing resistance and getting saturated, equivalent to open

circuit voltage at high resistance (10 MΩ). As a result, the instantaneous power density (P =

104
1 V2L
, where A is the effective area of PEH(10)) is reached up to 2.5 µW/cm2 at the resistance
A RL

of 750 kΩ (Fig. 4.9a).38

(a) (b)

Fig. 4.9 (a) Output voltage and instantaneous power density (circuit diagram is shown in the

inset) as a function of external load resistances under gentle finger touch and (b) Capacitor

charging performance of PEH(10).

Beside this, to investigate the energy storage capability of PEH(10), different capacitors were

charged up by connecting through typical full-wave four probe bridge rectifier circuit. Under

continuous dynamic tactile stimuli energy was stored in the capacitors (Fig. 4.9b) that can be

further used to drive several low power consumer electronics.39

4.3.4 Optical properties of MPC films

Furthermore, the good optical absorption ensures the photoresponse behaviour of MPC films

as illustrated in Fig. 4.10. It is found that MPC films exhibit the intense broad absorption

around 800 nm. It attributes to the fact that MAPI is responsible for this absorption as there is

a forbidden absorption in PVDF film.

105
 MPC(10)
MPC(1)
MPC(0.025)

Absorbance (a.u.)
PVDF

400 500 600 700 800 900

4.3.5 Photodetector performance

Thus photodetectors with MPC films have been fabricated as described in Fig. 4.11a and

recorded the current voltage (I-V) characteristic of the photodetector (PD) under dark and

light condition.

(a)

ITO coated Glass After etching of Casting of MPC

Glass ITO MPC

(b) (c)

Fig. 4.11 (a) Schematic of the photodetector fabrication and operation. Current-voltage

characteristic curves of (b) PD 0.025 and (c) PD 1.

106
The I-V characteristic of PD(0.025) and PD(1) show very low current value (Fig. 4.11b and

4.11c) under both dark and light condition, is might be due to the insulating behaviour of

PVDF that restricts the charge flow by breaking the interconnected network of

semiconducting MAPI. However, MPC(10) film made PD(10) shows effective change in I-V

characteristic between dark and light condition, thus becomes an effective photodetector.

(a) (b)

(d) (c)

Fig. 4.12 (a) Current–voltage characteristics of PD(10) under different light illumination. (b)

Current vs time curves with multiple cycle operation of PD(10) under the irradiance of 42.25

mW/cm2. (c) An enlarge view of photocurrent for rise and decay time calculation. (d)

Photocurrent response from PD(10) under illumination of light of different wavelength.

The I–V curves (Fig. 4.12a) both in dark and under light illuminations is almost linear

suggesting an Ohmic contact. It is obvious that photocurrent rises almost instantaneously

107
when the device is exposed to the light illumination. Under the light illumination, MAPI

absorbs the photons that generating electron-hole pairs those are separated by the external

electric field which conducts to the generation of photocurrent. Fig. 4.12b depicts the

photocurrent as a function of time (I-t curves) by illuminating the photodetector (PD(10))

with irradiance of 42.25 mW/cm2, while the bias voltage between two electrodes is kept

constant at 10 V. Light illumination was switched on and off periodically with an interval of

20 s by means of shutter to study the photoresponse of the photodetector. Instantly after

turning on the light, the photocurrent quickly arises and settles to a stable and saturated value.

Six repeated cycles are displayed in which the photocurrent is noticed to be consistent,

repeatable and responds to a similar fashion to light that exhibits good operation stability.

The time response speed is a key component for photodetectors for determining the ability of

a photodetector to follow fast changing optical signals.40 A quick photoresponse can be

assured clearly from the enlarged rising and decaying edges of photocurrent as shown in Fig.

4.12c.

The rising time and the decaying time are approximately 44 ms and 153 ms respectively,

pointing rapid photoresponse characteristic. Another important parameter of photo detector is

its spectral photo response. Being a low band gap (1.51 eV) materials, MAPI is able to absorb

full visible spectra and show photo response.

Three LEDs of light emission wavelengths 462, 520 and 630 nm were used to check spectral

response of the device. Fig. 4.12d shows the photo current produced by the device when

illuminated by pulsating LEDs of 10 millisecond pulse width while the device was biased at

10 V. The photo current values are normalized to 1 mW/cm2 incident optical light intensity.

Here we see that our device produces almost equal photo current for all three wavelengths

which confirms it’s capability of detecting light from all over the visible region. Generation

of slightly higher photo current when illuminated by lower wavelength (462 nm) may be

108
attributed to the enhanced transition probability of the electron from the valence band to the

conduction band for light with higher photon energy.41,42 Light of photon energy higher than

the band gap generates electron hole pair which increases conductivity of a photosensitive

material. Lower wavelength or higher energy pushes more number of electrons to the

conduction band which in turn increases photo current.

4.3.6 Photoactive piezoelectric energy harvester performance

Hence, MPC(10) becomes an excellent material for piezoelectric energy harvester and

photodetector application. This also supports the idea that MPC(10) could serve as a reliable

self-powered visible light detector. Thus, a hybrid device, i.e., photoactive piezoelectric

energy harvester (PPEH) has been prepared to use it for self-powered visible light detection.

(a) (b)

Fig. 4.13 (a) Change of piezoelectric response in terms of output voltage and (b) current on

excluding and illuminating of white light with continuous application and removal of stress.

The composite solution (which was also used to prepare MPC10 film) is casted on a

transparent flexible ITO coated PET substrate that serves as the top electrode. An adhesive

conducting carbon tape is attached on the other side that serves as the bottom electrode.

Finally, we encapsulate the whole device structure with PDMS, which kept the entire device

flexible and also add further protection to perovskite fillers from moisture. Piezoelectric

response from PPEH under periodic stress as a function of time is shown in Fig. 4.13. The

109
average peak value of the open circuit voltage decreases (Fig. 4.13a) under white light

illumination than in dark condition. In contrast, the short circuit current increases (Fig. 4.13b)

in light illumination than dark condition under the similar repeating stress.

PPEH

Dark Light

Fig. 4.14 Change in resistance on excluding and illuminating of white light with continuous

application and removal of stress.

This might be due to interaction with visible light electron-hole pairs are generated in MAPI

that gives rise to a photocurrent. This movement of electrons leading in the improvement of

local electromagnetic field, that could interrupts the dipole orientation in the composite

film.43 That results in voltage response reduction with respect to the response in the dark

condition.

The generated photocurrent created from extra charge carriers within the composite film

during photon excitation results in the enhancement of short circuit current. Thus, under

visible light, the internal resistance of the PPEH dropped to ∼294 kΩ from ∼326 kΩ (Fig.

4.14). The voltage and current output values are changed by 42 % and 39 % respectively in

comparison to without light illumination. Thus, PPEH could be attractive for futuristic self-

powered optoelectronic smart sensors and devices.43 In particular, it indicates that the PPEH

can also be used as a self-powered flexible visible light detector/sensor.

110
4.4 Conclusion

In summary, organo-lead halide perovskite material methylammonium lead iodide is

synthesized via co-precipitation method. The desirable amount of perovskite material

incorporation in PVDF can induce the stable electroactive β-phase, thus turns out an

attractive material for piezoelectric based energy harvesting applications. Therefore, the

traditional stretching and poling method can be avoided to polar phase induction in PVDF.

Furthermore, PVDF encapsulation prevents the degradation of MAPI and the resulting

composite film shows strong light absorption properties as well. In addition, MPC based

photodetectors show considerable performance with fast rising time that suggests that MPC

films may have promising applications as a photodetector. Thus MAPI incorporated PVDF

composite film promises the possibility of using as active material for multipurpose

application (such as mechanical energy harvester, photodetector and hybrid device, i.e.,

PPEH) which may have potential applications in the next generation of optoelectronic and

energy technologies. The coupling of the photoactive component with electroactive polymer

permits to detect visible light, which leads to significant change of piezoelectric output

voltage (∼42%) and current (∼39%). This result unambiguously suggests that PPEH can also

be employed as a self-powered flexible visible light detector.

4.5 References

[1] H.-S. Kim, C.-R. Lee, J.-H. Im, K.-B. Lee, T. Moehl, A. Marchioro, S.-J. Moon, R. H.

Baker, J.-H. Yum, J. E. Moser, M. Gra¨tzel, N.-G. Park, Sci. Rep., 2012, 2, 591.

[2] G. Hodes, Science, 2013, 342, 317–318.

[3] H. Zhou, Q. Chen, G. Li, S. Luo, T.-B. Song, H.-S. Duan, Z. Hong, J. You, Y. Liu, Y.

Yang, Science, 2014, 345, 542–546.

[4] P. K. Nayak, D. Cahen, Adv. Mater., 2014, 26, 1622–1628.

111
[5] L. J. Phillips, A. M. Rashed, R. E. Treharne, J. Kay, P. Yates, I. Z. Mitrovic, A.

Weerakkody, S. Hall, K. Durose, Sol. Energy Mater. Sol. Cells, 2016, 147, 327–333.

[6] S. D. Wolf, J. Holovsky, S.-J. Moon, P. Löper, B. Niesen, M. Ledinsky, F.-J. Haug, J.-H.

Yum, C. Ballif, J. Phys. Chem. Lett., 2014, 5, 1035−1039.

[7] Y. Wang, Y. Zhang, P. Zhang, W. Zhang, Phys. Chem. Chem. Phys., 2015, 17,

11516−11520.

[8] Q. Chen, N. D. Marco, Y. M. Yang, T.-B. Song, C.-C. Chen, H. Zhao, Z. Hong, H. Zhou,

Y. Yang, Nano Today, 2015, 10, 355−396.

[9] J. Xiong, B. Yang, C. Cao, R. Wu, Y. Huang, J. Sun, J. Zhang, C. Liu, S. Tao, Y. Gao, J.

Yang, Org. Electron., 2016, 30, 30−35.

[10] D. Koushik, W. J. H. Verhees, Y. Kuang, S. Veenstra, D. Zhang, M. A. Verheijen, M.

Creatore, R. E. I. Schropp, Energy Environ. Sci., 2017, 10, 91-100.

[11] G. Niu, W. Li, F. Meng, L. Wang, H. Dong, Y. J. Qiu, Mater. Chem. A, 2014, 2, 705–

710.

[12] M. M. Alam, S. K. Ghosh, D. Sarkar, S. Sen, D. Mandal, Nanotechnology, 2017, 28,

015503.

[13] P. Martins, A. C. Lopes, S. L. Mendez, ‎Prog. Polym. Sci., 2014, 39, 683–706.

[14] B. Saravanakumar, S. Soyoon, S.-J. Kim, ACS Appl. Mater. Interfaces, 2014, 6,

13716−13723.

[15] D. Mandal, S. Yoon, K. J. Kim, Macromol. Rapid Commun., 2011, 32, 831–837.

[16] A. J. Lovinger, Science, 1983, 220, 1115–1121.

[17] D. Mandal, K. Henkel, D. Schmeißer, Mater. Lett., 2012, 73, 123–125.

[18] D. Miranda, V. Sencadas, A. S. Iglesias, I. P. Santos, L. M. L. Marzán, J. L. G. Ribelles,

S. L. Mendez, J. Nanosci. Nanotechnol., 2009, 9, 2910–2916.

112
[19] S. K. Ghosh, A. Biswas, S. Sen, C. Das, K. Henkel, D. Schmeisser, D. Mandal, Nano

Energy, 2016, 30, 621–629.

[20] D. Chen, T. Sharma, J. X. J. Zhang, Sens. Actuators, A, 2014, 216, 196–201.

[21] Y. Yuan, T. J. Reece, P. Sharma, S. Poddar, S. Ducharme, A. Gruverman, Y. Yang, J.

Huang, Nature mater., 2011, 10, 296-302.

[22] S. B. Lee, S. C. Yoon, P. S. Kim, S. Park, J. Lim, C. S. Yoon, Appl. Phys. Lett., 2014,

104, 083302.

[23] C. Xu, Z. L. Wang, Adv. Mater., 2011, 23, 873–877.

[24] Y. Yang, H. Zhang, Y. Liu, Z.-H. Lin, S. Lee, Z. Lin, C. P. Wong, Z. L. Wang, ACS

Nano, 2013, 7, 2808–2813.

[25] G. C. Yoon, K.-S. Shin, M. K. Gupta, K. Y. Lee, J.-H. Lee, Z. L. Wang, S.-W. Kim,

Nano Energy, 2015, 12, 547–555.

[26] C. Xu, X. Wang, Z. L. Wang, J. Am. Chem. Soc., 2009, 131, 5866–5872.

[27] M. I. Saidaminov, A. L. Abdelhady, B. Murali, E. Alarousu, V. M. Burlakov, W. Peng,

I. Dursun, L. Wang, Y. He, G. Maculan, A. Goriely, T. Wu, O. F. Mohammed, O. M. Bakr,

Nat. Commun., 2015, 6, 1–6.

[28] S. Chen, J. Briscoe, Y. Shi, K. Chen, R. M. Wilson, S. Dunna, R. Binions, Cryst Eng

Comm., 2015, 17, 7486–7489.

[29] D. Mandal, K. Henkel, D. Schmeisser, J. Phys. Chem. B, 2011, 115, 10567–10569.

[30] S. Ramasundaram, S. Yoon, K. J. Kim, C. Park, J. Polym. Sci. Part B: Polym. Phys.,

2008, 46, 2173–2187.

[31] A. C. Lopes, S. A. C. Carabineiro, M. F. R. Pereira, G. Botelho, S. L. Mendez, Chem

Phys Chem., 2013, 14, 1926–1933.

[32] S. K. Ghosh, M. M. Alam, D. Mandal, RSC Adv., 2014, 4, 41886–41894.

[33] D. M. Esterly, B. J. Love, J. Polym. Sci. Part B: Polym. Phys., 2004, 42, 91–97.

113
[34] J. S. Manser, M. I. Saidaminov, J. A. Christians, O. M. Bakr, P. V. Kamat, Acc. Chem.

Res., 2016, 49, 330−338.

[35] S. K. Ghosh, T. K. Sinha, B. Mahanty, D. Mandal, Energy Technol., 2015, 3, 1190–

1197.

[36] D. Chen, M. Hang, K. Chen, K. Brown, J. X. J. Zhang, IEEE SENSORS, Busan, 2015,

1–4.

[37] A. Sultana, M. M. Alam, S. Garain, T. K. Sinha, T. R. Middya, D. Mandal, ACS Appl.

Mater. Interfaces, 2015, 7, 19091−19097.

[38] A. Sultana, M. M. Alam, A. Biswas, T. R. Middya, D. Mandal, Transl. Mater. Res.,

2016, 3, 045001.

[39] S. Niu, X. Wang, F. Yi, Y. S. Zhou, Z. L. Wang, Nat. Commun., 2015, 6, 8975–8983.

[40] S. Yang, S. Tongay, Q. Yue, Y. Li, B. Li, F. Lu, Sci. Rep., 2014, 4, 5442.

[41] O. L. Sanchez, D. Lembke, M. Kayci, A. Radenovic, A. Kis, Nat. Nanotechnol., 2013, 8,

497–501.

[42] P. A. Shaikh, D. Shi, J. R. D. Retamal, A. D. Sheikh, M. A. Haque, C.-F. Kang, J.-H.

He, O. M. Bakr, T. Wu, J. Mater. Chem. C, 2016, 4, 8304–8312.

[43] T. K. Sinha, S. K. Ghosh, R. Maiti, S. Jana, B. Adhikari, D. Mandal, S. K. Ray, ACS

Appl. Mater. Interfaces, 2016, 8, 14986−14993.

114