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Comparative Study on Flexible ZnO Based Nano-Generator Using

Schottky and p-n junction Contact for Energy Harvesting
Received 00th January 20xx,
Accepted 00th January 20xx
Applications
Kirubaveni Savarimuthu,a Radha Sankararajan, a Govindaraj Rajamanickam and b Santhosh

Nanoscale Accepted Manuscript

DOI: 10.1039/x0xx00000x
Narendhiran, b
www.rsc.org/

Though the piezoelectric and triboelectric nano generators

Vibration based piezoelectric energy harvesting from unused derive the same excitation method, the piezoelectric method
ambient sources is an efficient approach for battery-free, has an inherent property of influencing the electronic and
sustainable and green power source for self-powered electronics. opto-electronic properties. The application of such nano-
This paper presents the performance enhancement of a p-n generator can be extended to piezo electronics and opto-
junction based flexible nano-generator (NG). A stable, non-
piezoelectronics7.The piezoelectric energy harvesting (PEH) is
hazardous Spiro and Zinc Oxide (ZnO) p-n junction based NG is
proposed. The device performance is compared with Schottky highly preferred due to its dynamic response and high energy
contact based NG. The experimental study is carried out using tip density.
excitation method. Most importantly, the contact modification In recent times, lead free piezoelectric material such as
with Spiro improves the performance of the device by five times ZnO based micro and nano devices are in demand for a wide
thereby yielding an open circuit voltage of 300 mV, short-circuit range of applications, as it exhibits both piezoelectric and
-2
current density of 220 µAcm and maximum power density up to semiconducting properties. The reason for choosing ZnO as a
-2
48 µWcm at 0.5 N. Further, the performance enhancement is potential material is due to its bio safe nature, exhibits both
achieved by reducing the external screening and the internal 8
piezoelectric and semiconducting properties , most diverse
impedance. The results are validated using RC time constant value 9
and abundant configurations of nanostructures , synthesised
derived from the impedance analysis.
using low temperature and simple hydrothermal technique.
The first self-powered ZnO nanowires (NW) array is
10
Introduction developed by Wang et al . From the research, it is evident
that these NGs rely on the voltage generated by the NWs
The rapid expansion in the demand for low power and
through an external force as it induces a dynamic strain, which
portable devices leads to the proliferation in the field of
results in a transient flow of electrons in the load. The ZnO
energy harvesting devices. From the literature it is evident that
NW/Nanorods (NRs) are widely drawing interest due to its 1D
the vibration sources can be used as mechanical source to structure, high sensitivity to small force and large deformation.
generate energy, due to its constant availability1. Several types The ZnO nanorods are synthesized using hydrothermal based
2 3
of nano-electric generators like piezoelectric , triboelectric , chemical methods, which are most advantageous due to its
4 5
pyroelectric , thermoelectric are reported in the literature. simplicity, convenience, low cost and growth at relatively
11-12
Piezoelectric method of energy generation is experimented in lower temperature .
this research article and the results are reported. Unlike the The researches about the fabrication of NG on the rigid
13-14
pyroelectric and thermoelectric nano-generator, which substrate are wide .The flexible nano-generators reported
15-16
predominantly depends on time-dependent temperature in literature use polymers which cannot withstand high
change or temperature gradient existing in the devices, the temperature during annealing. Therefore the internal
proposed solution used the mechanical energy that exists in its screening is high for such devices. In order to avoid this,
own form in nature. On the other hand, the triboelectric nano- kapton is used as the substrate. Piezoelectric NG requires a
generator uses the contact electrification effect and it requires high quality Ohmic and/or Schottky or p-n junction contact
electrostatically charged material to causes a potential .
6 between the ZnO nanorods and top/bottom electrode. Initially
Schottky contact is considered to be essential for the devices
to work. Moreover, it is observed that the peak voltage
17-18
generation from Schottky contact based devices is limited
to a few hundred mV. Furthermore, the Schottky contact with

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19
intermediate insulator is proposed for improved technique is used, where the input force is more controllable
performance. Later, p-n junction based NG is proposed by and measurable.
20
Briscoe et al . It employs poly 3,4-ethylenedioxythiophene The rest of the manuscript is organized as follows: Section
poly styrene sulfonate (PEDOT:PSS) polymer as p-type layer II presents the experimental methodology. Section III presents
coated over ZnO. PEDOT:PSS has high acidity, which corrodes various characterization of the NG. The performance of the
the underlying Indium Tin Oxide (ITO) electrode and might device is evaluated and compared in section IV.
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cause device degradation. It is also hygroscopic and can only

withstand temperature of about 150˚C. Hence there is a need
for more stable p-type layer. Spiro is one such alternate p-type Experimental Methodology
21
layer, which is more stable till 350˚C . In the fabrication of the NG, initially ITO is sputtered over
The present work demonstrates the fabrication of ZnO- kapton in which ZnO seed layer is spin coated. The ZnO
Spiro based p-n junction contact NG. Its performance is nanorods are grown using hydrothermal method. After the
compared with a metal-insulator-semiconductor Schottky growth of nanorods, PMMA/spiro is spin coated for developing
contact based NG. Annealing of ZnO suppresses the defects an insulating/p-type layer between the top electrode and ZnO

Nanoscale Accepted Manuscript

and impurities, thus reducing the internal screening. External rods. The top electrode is created by sputtering Ag. The
screening is reduced by having an insulating poly methyl process flow of the developed energy harvester is shown in
methacrylate (PMMA) layer in Schottky contact and hole Fig.1.
collecting Spiro layer in p-n contact devices. A complete The synthesis of nanorods and coating of PMMA is based
mechanical and electrical characterization is performed for the 25
on the previous research . To obtain Spiro layer, 72 mg of
proposed NG. Spiro-OMeTAD (solaronix) is dissolved in 1 ml of
The initial measurements of voltage from strained ZnO chlorobenzene. The deposition of spiro solution is carried out
nanorods are done by deflecting single rods using an atomic- using spin-coating technique at 2000 rpm for 30 seconds. Four
force microscope (AFM) tip. There are many potential issues layers of spiro having 500 nm (measured using Dektak XT,
because the contact is not available all the time during output Bruker) thickness each are then deposited onto the nanorods
measurement22. Testing of the voltage and current output layer. After each deposition, the substrate is heated at 100°C
from nanostructure expanded from single-rod to nanorods for 10 min. The next process involves the DC magnetron
array testing. Testing of arrays on rigid substrates is largely sputtering of Ag over the PMMA/Spiro layer. From the
confined to acoustic excitation. For flexible substrate optimized process parameters, the deposition is done for 4
compression of the nano structured array by manual pressing minutes to get 400 nm thin film of Ag with a sheet resistance
on the top layer is reported23-24. But there is no control over of 3Ω/ square meter.
the input force. Hence in this paper, a simple tip excitation

Fig. 1 Process flow of NG synthesi

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−1
Characterization of Nanogenerator stretching frequency of CH3. The band at 1319 cm is due to
-1
the C–N stretching frequency. The peaks at 1465 cm , 1177
-1 26
cm is due to C-H bending vibration .
The morphology of the prepared ZnO NRs on Kapton/ITO is
analyzed using Field Emission Scanning Electron Microscope
(FE-SEM) (HITACHI SU6600), Fourier-transform infrared FE-SEM
spectroscopy (FTIR) is analyzed using the Alpha T, Bruker, USA.

Nanoscale Accepted Manuscript

A FE-SEM image of the vertical c-axis oriented hexagonal
The I-V characterization is performed using Keithley 6487 Wurtzite ZnO nanorods having length 1.7 µm is shown in Fig. 3.
source meter. The tilting in the growth of nanorods arises from seed layer
texturing. Fig. 3 (a) is the top view of the NRs at the
magnification of ×50 K.The cross section of the NR is shown in
FTIR Fig. 3(b). Fig. 3(c) shows top view of ZnO/Spiro. It clearly
identifies the uniform and dense coating of Spiro.
The FTIR spectrum of ZnO nanorods in the range of 500-4000
–1
cm is obtained at room temperature and is shown in
–
Fig. 2 (a). The spectrum depicts transmittance around 565 cm
1
, which is the distinctive characteristic of Wurtzite hexagonal
phase pure ZnO. Fig. 2 (b), shows the presence of distinct
−1 −1
absorption band from 1150 cm to 1250 cm , which is
attributed to the C–O–C stretching vibration. The band at 1062
−1 26
cm is the characteristic peak of PMMA .

(a)

Fig. 2. FTIR spectrum a. ZnO NR’s/ITO/Kapton b. PMMA/ZnO

NR’s/ITO/Kapton c. Spiro/ZnO NR’s/ITO/Kapton

Figure 2 (c) shows the FTIR spectrum of the Spiro. Fig. 2 (c)
−1
clearly shows the presence of a distinct peak at 1035 cm and
−1
1244 cm , which are attributed to the C–O–C symmetric and
asymmetric stretching frequency respectively. The band at
−1 −1 −1
3038 cm , 1465 cm and 1508 cm are related to the CH, C-
C, C=C stretching frequency of aromatic ring. The band at 2833
−1
cm shows the existence of the methyl group C-H stretching.
−1
The band at 2948 cm shows the presence of asymmetric
(b)

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I  I e  1e   (1a)



I  I e   1 (1b)

2.5
Dark

Nanoscale Accepted Manuscript

Photo

Current Density (mA/cm2)

2

1.5

0.5

0
0 0.5 1 1.5
Voltage (V)
(c)

Fig.3. FE-SEM images (at the magnification of x 50K) (a) Annealed ZnO NRs
(a)
(top view) (b) Cross section of ZnO NRs and (c) Spin coated Spiro

90
I-V curve Dark
Current Density (mA/cm2)

75 Photo
I-V characterization is carried out on the fabricated devices to
confirm the Schottky and p-n junction behaviour. Fig.4 (a) 60
shows the J-V characteristic of PMMA coated device and Fig.4
45
(b) shows the J-V characteristic of Spiro coated device for the
voltage range of -1.5 V to +1.5V. The curve is non-linear due to 30
exponential increase in its forward current with respect to the
15
operating voltage. The corresponding forward resistance (Rfrd)
and reverse resistance (Rrev)27 of the NG’s at ∆V = 0.3 V are 0
0 0.5 1 1.5
tabulated in Table 1.
Voltage (V)
Table 1: I – V characteristics of the nanogenerator

(b)
Parameters ZnO/PMMA ZnO/Spiro
Fig.4. Current– voltage characteristics of the a. Ag/n-ZnO Schottky contact b.
Forward Resistance Rfrd (Ω) 333 5.45
Spiro/ ZnO p-n contact ZnO Nanogenerator
Reverse Resistance Rrev (KΩ) 3 0.18
Current Rectification Ratio 18 16
Diode Turn-on Voltage (V) 0.7 0.5 The method to determine ideality factor (n), reverse saturation
Reverse Leakage Current Density 1.1 0.4 current (I ) and zero-bias barrier height (Ф ) are reported in
25
(mAcm-2) literature . After the least square fit in the experimental data
as in Fig.5, the value of n, I , Ф of p-n contact based NG is
determined to be 3.8, 2.74 mA and 0.53 eV. The values of
28
For the Schottky barrier and p-n junction contact , the n, I , Ф of Schottky contact based NG is determined to be
relation between the forward voltage (V) and forward current 7.27, 3.7483 µA and 0.1971 eV. The deviation of the ideality
(I) is expressed respectively as

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factor is due to the influence of interfacial layers and surface Power Measurements
states.
The power generated by the NG is calculated using,


P (7)


Where P is the power and V is the peak voltage measured

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across the load. According to maximum power transfer

theorem, maximum output is obtained at impedance matching
condition. From Fig. 8 (a) and (b) the impedance matching
occurs at 10 kΩ and 1 kΩ respectively for ZnO/PMMA and
ZnO/Spiro. From the Fig. 8 it is evident that the p-n based NG
performs five times better than Schottky contact based NG
yielding maximum power density of 48 µWcm-2.

Nanoscale Accepted Manuscript

Fig.5 lnI-V plot of the Spiro/ ZnO p-n contact

Performance Evaluation
This section presents the performance metrics such as of
open-circuit voltage (Voc), short-circuit current (Isc), power
density, impedance analysis and mechanical characterization
for the fabricated energy harvester using tip excitation
techniques. (a)

Measurement of open-circuit voltage (Voc) and short-circuit

current (Isc)

The experimental set-up and the block diagram for evaluating

the NG are shown in Fig. 6(a) and 6(b) respectively. The
piezoelectric NG is placed in the aluminium cantilever of
dimension 250 mm× 15 mm× 0.5 mm. An electromagnet of
length 16 mm (Le) with 2000 coil turns (N) having a cross
2
sectional area of 78 mm (A) is placed at the free end of the
beam for the excitation of the beam. The flux density of the
cylindrical permanent magnet Br is 1.1T, length Lr=3 mm,
radius R=5 mm and the initial gap between the magnets, d=30
mm. (b)
Fig. 6 Experimental set-up (a) Photograph (b) Block Diagram
Piezoelectric NG is bonded on the top surface of the cantilever
at a distance of 5 mm from the fixed end. The proposed PN Impendence Analysis
and Schottky based energy harvesters are set to vibrate with a
help of an electromagnetic excitation. The frequency of The impedance analysis of the devices is performed from
excitation is about 12 Hz and it is the fundamental natural 100 Hz – 1 MHz using electrochemical workstation (V3-500,
frequency of an individual cantilever for an excitation Ametek, USA). Fig. 9 (a) and (b) shows the Nyquist plot of the
magnitude of 0.5 N. The output voltage of 400 mV and 300 mV NG obtained using the complex impedance response at a
are generated at 0.5 N for Schottky contact and p-n contact mentioned input frequency range. A semi-circular arc shaped
29-30
based NG respectively as shown in Fig. 7(a) and (b). The plot indicates the presence of an RC circuit . The RC time
constant (TRC) is given by,
deviation in the output frequency is attributed to the variation
in the bonding thickness between the device and the T  (8)
cantilever. The measured current levels are shown in Fig. 7(c) 

and (d).
The TRC is evaluated from the arcs labelled with their resonant
frequencies, fr. The duration for which ZnO nanorods retains

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its piezoelectric charge until they are completely screened is from the power density–resistance relationship. Being an
related to TRC. The measured value of TRC for PMMA device is insulator, the resistivity of PMMA is considerably higher than
0.079 ms and for Spiro device is 0.327 ms. This shows the the semiconducting Spiro. Hence makes the difference in
increase in charge storage in the piezoelectric device. The impedance between the devices. For an RC circuit, ZIm is
internal resistance is approximated from the diameter of the maximum at the critical or resonant frequency (fr), which is 2
curve along the axis denoting the real component of the kHz for PMMA and 486 Hz for Spiro device. At this frequency,
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impedance (ZRe) as, the RC impedance is purely resistive at low

"
frequency. This gives internal resistance (Rint) value of RC  (9)
#$%
approximately 21 kΩ for PMMA device and 1.2 kΩ for Spiro
device. This is consistent with the resistance values derived

Voltage Output With Excitation

400 Without Excitation

Open circuit voltage (mV)

300

Nanoscale Accepted Manuscript

200
100
0
-100
-200
-300
-400
0 0.5 1 1.5 2 2.5 3 3.5 4 4.5 5 5.5 6 6.5
Time (sec)

Output Voltage With excitation

400
Open circuit voltage(mV)

Without excitation
300
200
100
0
-100
-200
-300
-400
0 0.05 0.1 0.15 0.2
Time (sec)
(a)

Output Voltage With Excitation

450 Without Excitation

350
250
Voltage (mV)

150
50
-50
-150
-250
-350
-450
0.0 0.5 1.0 1.5 2.0 2.5 3.0 3.5 4.0 4.5 5.0 5.5 6.0
Time (Sec)

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450
With Excitation
350
250 Without Excitation

Voltage (mV)
150
50
-50
-150
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-250
-350
-450
0.0 0.1 0.1 0.2 0.2 0.3
Time (Sec)

(b)

Nanoscale Accepted Manuscript

20 250
15
150

Current (µA)
10
Current (µA)

5 50
0
-50
-5
-10 -150
-15
0 0.1 0.2 0.3 0.4 -250
0.00 0.05 0.10 0.15 0.20
Time (Sec)
Time (sec)
(c) (d)

Fig.7 Performance evaluation a. Open-circuit voltage recorded for continuous excitation with enlargement view of ZnO /PMMA/ Ag device [16] b. Open-
circuit voltage recorded for continuous excitation with enlargement view of ZnO /Spiro/ Ag device c. Current across 10 kΩ Open-circuit voltage of ZnO
/PMMA/ Ag device d. Current across 1 kΩ Open-circuit voltage of ZnO /Spiro/ Ag device.

60
10
9 50
Power Density (µW/cm2)
Power Density (µW/cm2)

8
7 40
6
5 30

4
20
3
2 10
1
0 0
0.1 1 10 100 1000 0.1 1 10 100 1000
Load Resistance (kΩ) Load Resistance (kΩ)

(a) (b)

Fig.8 Resistive load match measurement a. ZnO /PMMA/ Ag device b. ZnO /Spiro/ Ag device

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Nanoscale Accepted Manuscript

(a)
Fig. 10 Stress-Strain Curves

Output Voltage
450
With
350 Excitation
250

Voltage (mv)
Without
150 Excitation
50 30000
-50
-150
-250
-350
-450
0.0 2.0 4.0 6.0 8.0

(b)
Time (Sec)
Fig. 11 Mechanical stability in output voltage generation
Fig. 9 Nyquist plot for ZnO NG (a) ZnO/PMMA (b) ZnO/Spiro.

From this the internal capacitance (Cint) is calculated as 3.79 nF

Further, the estimated key performance parameter of the
for PMMA device and 272 nF for Spiro device.
fabricated NG is tabulated in Table 2.
Mechanical Characterization Table 2: Performance parameter of the nanogenerator
The mechanical properties of the ZnO/PMMA and ZnO/Spiro
Parameters ZnO/PMMA ZnO/Spiro
films are explored from stress-strain measurements at room
Open circuit voltage Voc (mV) 400 300
temperature as shown in Fig. 10. The Young’s modulus is
Optimum load R (kΩ) 10 1
estimated by considering the stress-strain slope for the linear
32 Voltage on optimum load 304 220
portion of the curve . ZnO/PMMA and ZnO/Spiro possesses
(mV)
32 MPa and 48 MPa of Young’s modulus respectively. This
Current density on optimum 30 220
reveals better resistance of ZnO/Sprio device compared to the load (µAcm-2)
ZnO/PMMA device to the deformation under loaded Instantaneous area power 9 48
condition. Thus, a substantial improvement in the mechanical density (µWcm-2)
properties leads to an enhanced electrical performance of the Approximate internal 21 1.2
spiro devices. From the experiment above, the proposed spiro impedance Rint (real, kΩ)
device has a higher stability over 30000 cycles in the Approximate internal 3.79 nF 1.09 pF
generation of output voltage without any degradation as capacitance Cint
evident from Fig. 11. Thus the proposed energy harvester is Resonant Frequency (Hz) 2000 486
highly durable and can be used in autonomous electronic TRC (msec) 0.079 0.327
devices. Young’s Modulus (MPa) 32 48

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(a) (b) (c)

Ec : conduction band edge. Ev : valence band edge. Edp : depolarisation field. Ebar : Barrier field

Fig 12.Energy band evolution for a ZnO – Sipro device (a) At Equilibrium condition. (b) After stress is applied ZnO bands are tilted due to depolarisation
field (Ebar) and screening of the positive polarization charges (c) Accumulation of holes near depletion region and screening of the negative polarization
charges22.
Plastic/ZnO/PEDOT:PSS 9.6 13.1 0.126 [20]

Energy band Evolution PET/ZnO/CuSCN/ 1070 1880 434 [29]

PEDOT:PSS
Cu/ZnO power/Al 740 12 8.97 [31]
To understand the voltage and current generation in the NG Kapton/ZnO/PMMA 400 30 9 This
the piezoelectric polarization effect is shown in the energy work
band diagram. Fig. 12(a) shows the p-n junction contact at Kapton/ZnO/Spiro 300 220 48 This
equilibrium position. Fig. 12(b) shows the band diagram after work
applying vibration. When strained, polarization charges
develop at the contact. These unscreened charges leads to Though [19] and [29] describes a high power density, there are
depolarization field (Edp), which drives the screening charges some shortcomings as detailed below.
both at the contact (external Screening) and within the In [19], the performance of the harvester is
material (internal screening). Edp cause the free electrons in increased by stacking more than 10 devices to obtained large
the ZnO to screen the positive polarization charges at the electrical output. This makes the entire system bulky. Similarly
metal. Fig.12 (c) shows the screening of negative polarization in [29], the authors have used an additional passivation layer
charges by the accumulation of the holes in the Spiro because (CuSCN) to improve the performance. However the passivation
of Edp. Unlike Spiro, the insulating properties of PMMA would layer used is toxic when compared to other polymers.
not exhibit screening effect. Hence PMMA will not transfer
charge carriers. Therefore, the rate of external screening in
case of Spiro devices is faster than PMMA devices. Table 3 Conclusion
shows the Comparison with the existing state of the art. Growth of dense ZnO nanorods on a flexible substrate using
hydrothermal method is presented. The contact
characteristics, ohmic contact at ITO/ZnO, while Schottky
Table 3: Comparison with the existing state of the art contact (SIM) at ZnO/Ag and p-n contact at ZnO/Spiro are
Power demonstrated from I-V measurements. By tip excitation
ISC (μA technique, performance of both the devices is systematically
Device VOC (mV) density Ref
cm-2) analyzed and compared. The impact of contact in the
(μW cm-2 )
reduction of external screening is explored. Thus, despite of
Kapton/ZnO/Au 2100 0.105 300 [19]
having a higher Voc of 400 mV, PMMA device has a maximum
PET/ZnO/PMMA 252 1.58 0.243 [30] instantaneous power density of 9 µWcm-2 compared to Voc of
300 mV, and power density of 48 µWcm-2 for a spiro device.
PET/ZnO/PEDOT: PSS 90 474 36 [30] This is because Rint of PMMA device is 18 times higher than
spiro device.

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Reference [31] Al-Ruqeishi, M. S., Mohiuddin, T., Al-Habsi, B., Al-Ruqeishi, F., Al-Fahdi,
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[32] Rahman, W., Ghosh, S.K., Middya, T.R. and Mandal, D, Materials
Research Express, 2017, 4(9), p.095305.
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[3] Gu, G.Q., Han, C.B., Lu, C.X., He, C., Jiang, T., Gao, Z.L., Li, C.J., Wang,
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