Int. J. Nanotechnol., Vol. 19, Nos.

2/3/4/5, 2022 223

Encapsulation of Ag nanoparticle-carbon composite

and enhancement of visible light ZnO nanorods
photodiode

Suvindraj Rajamanickam,
Sabah M. Mohammad* and Z. Hassan
Institute of Nano Optoelectronics Research and Technology (INOR),
Universiti Sains Malaysia,
11800 Penang, Malaysia
Email: gazers22@gmail.com
Email: sabah@usm.my
Email: zai@usm.my
*Corresponding author

Aminu Muhammad
Institute of Nano Optoelectronics Research and Technology (INOR),
Universiti Sains Malaysia,
11800 Penang, Malaysia
and
Department of Physics,
Sule Lamido University Kafin-Hausa,
Jigawa State, 741103, Nigeria
Email: aminumuhammad1427@gmail.com

E.A. Kabaa
Institute of Nano Optoelectronics Research and Technology (INOR),
Universiti Sains Malaysia,
11800 Penang, Malaysia
Email: uummddaa@gmail.com

Abstract: Surface modification on zinc oxide nanorods (ZnO NRs) by

encapsulating with silver nanoparticles-carbon (Ag NPs-C) composite was
done and its characterisation was undertaken. Field emission scanning electron
microscopy (FESEM) shows a thin film of Ag NPs-C encapsulating the ZnO
NRs. Diffuse reflectance spectroscopy (DRS) shows Ag NPs-C has higher
reflectance in the 320–380 nm range, with a small absorption peak at 320 nm
due to Ag NPs plasmonic effect. ZnO NRs encapsulated with the composite
records a broader peak and slight red shift in the photoluminescence (PL)
spectra. The composite encapsulating the ZnO NRs introduces new energy
states in the ZnO lattice structure, resulting in the encapsulated ZnO NRs more
photosensitive to longer wavelength (460 nm) compared to unencapsulated
ZnO NRs which is more photosensitive to ultraviolet wavelength (395 nm).

Copyright © 2022 Inderscience Enterprises Ltd.

224 S. Rajamanickam et al.

Keywords: zinc oxide; Ag-NPs-carbon composite; visible light photodiode;

I-V characterisation; I-t characterisation; ZnO nanorods encapsulation.

Reference to this paper should be made as follows: Rajamanickam, S.,

Mohammad, S.M., Hassan, Z., Muhammad, A. and Kabaa, E.A. (2022)
‘Encapsulation of Ag nanoparticle-carbon composite and enhancement of
visible light ZnO nanorods photodiode’, Int. J. Nanotechnol., Vol. 19,
Nos. 2/3/4/5, pp.223–232.

Biographical notes: Suvindraj Rajamanickam received his Bachelor’s degree

in Pure Science (Physics) from Universiti Sains Malaysia in 2018 and is
currently pursuing his Master’s degree in Optoelectronics with the Institute of
Nano Optoelectronics Research and Technology (INOR), Universiti Sains
Malaysia. His current research interests include thin film fabrication and
characterisation, nanostructures and organic materials in optoelectronics
application.

Sabah M. Mohammad is currently serving as a Senior Lecturer at Institute of

Nano Optoelectronics Research and Technology (INOR), Universiti Sains
Malaysia (USM). During 2018, he was working as Teaching fellow at INOR-
Universiti Sains Malaysia (USM). He also has authored over 38 academic
papers and patent related to his research area. In 1991, he received his
Bachelor’s degree in Science (BSc), Physics, at the school of physics,
Salahaddin University, Iraq (SUI). In 2013, he received his Master (MSc)
degree in the Solid State, at the School of Physics, USM. He completed his
PhD degree in 2017, at the School of Physics, USM. His Doctorate was in the
Solid State with the research area of “Applied and engineering physics”,
[Semiconductor of fabrication (thin Film, Epitaxy and Nano Structured)]. The
title of his thesis was “Growth of ZnO Nanorods Using Hydrothermal and
Modified Chemical Deposition for Devices Applications”.

Z. Hassan is currently the Director of the Institute of Nano Optoelectronics

Research and Technology (INOR), at the Universiti Sains Malaysia.
She received her PhD degree in Experimental Condensed Matter Physics from
Ohio University, USA in 1998. Her focus of research is on all aspects related to
materials growth, characterisation, and fabrication of optoelectronic and
electronic devices such as LEDs, sensors and solar cells. She has been a
pioneer researcher in Malaysia on work related to GaN-based materials and
devices.

Aminu Muhammad received his BSc (Hons) in Physics and MSc in Physics
from Bayero University Kano, Nigeria in 2011 and 2016, respectively. He is
currently a Doctoral candidate at the Institute of Nano Optoelectronics
Research and Technology (INOR), Universiti Sains Malaysia. His current
research interests focus on the synthesis and characterisation of semiconductor
oxide materials for optoelectronics application. He is a research
Assistant/Lecturer at the Department of Physics, Sule Lamido University,
Kafin-hausa, Nigeria.

E.A. Kabaa is a PhD student in Institute of Nano Optoelectronics Research and

Technology (INOR)/Universiti Sains Malaysia who received his MD degree
from Universiti Sains Malaysia School of physics. He is a senior physicist in
Ministry of Oil in Iraq. He has many publications in bio-chemical sensors
based EGFET. He also participated in several international conferences.
 Encapsulation of Ag nanoparticle-carbon composite and enhancement 225

This paper is a revised and expanded version of a paper entitled ‘Encapsulation

of Ag nanoparticle-carbon composite and enhancement of visible light ZnO
nanorods photodiode’ presented at the 5th Meeting of Malaysia Nitrides
Research Group (MNRG 2020), Virtual Conference, 1–2 December, 2020.

1 Introduction

Zinc oxide (ZnO) is a very versatile material in the field of optoelectronics, seeing many
uses such as in chemical sensors, gas sensors, pH sensors, ultraviolet (UV) light-emitting
devices (LEDs) and UV photodetectors [1]. ZnO is an n-type semiconductor having a
hexagonal wurtzite type structure, large exciton binding energy of 60 meV at room
temperature and direct band gap of 3.37 eV, which makes ZnO a perfect material for
fabricating UV photodetectors [2]. One-dimensional ZnO nanostructures such as
nanorods and nanowires are better suited than two-dimensional ZnO structures in UV
photodetectors because their high surface to volume ratio, high optical gain and response
and high crystallinity [3]. ZnO nanorods can be fabricated by many methods such as
chemical vapour deposition, thermal evaporation, microwave irradiation and magnetron
sputtering which produces high crystalline ZnO nanorods however it comes at a cost of
being expensive to produce and inflexible experimental conditions [4]. Solution based
methods such as the hydrothermal method and chemical bath deposition (CBD) has been
gaining traction in research due to its simplicity and low toxicity [5]. To improve the
performance of ZnO photodetectors, many researchers have modified the ZnO
photodetectors with metallic nanoparticles (NPs) [6–9]. A recent innovation of ZnO UV
photodetectors was done by Wang et al. [10] who fabricated silver (Ag) NPs modified
ZnO UV photodetector by inkjet printing. The Ag NPs are expected to passivate surface
defects in ZnO structures and improves the photodetector performance by decreasing the
dark current and decay time of the photodetector [10]. In addition to that, the surface
plasmon effect of Ag NPs will enhance the photocurrent of the photodetector. Ag NPs are
interesting NPs that have many usages in life and there are many pathways to synthesise
Ag NPs such as by physical methods (laser ablation method, arc discharge, spray drying,
pulsed electron evaporation), chemical reduction methods whereby the chemical
reductions occurs in solution resulting in colloids, green methods and photoreduction
methods [11]. Liu et al. [12] modified a ZnO UV photodetector to be sensitive to visible
light by doping ZnO with carbon (C), with the carbon-doped ZnO nanostructures
synthesised on carbon cloth by carbothermal evaporation process. We hope to emulate
his work using a simple and low-cost method using cheaply obtained source materials.
In this work, we deposited Ag NPs-carbon composite on ZnO NRs to encapsulate the
top of the nanorods and study its effect on ZnO photodetector performance. The
morphological, optical and electrical properties of this encapsulated ZnO nanorods will
be compared to another similar sample without encapsulation.

2 Experimental

Firstly, p-type silicon wafer substrates (111) were cleaned using Radio Corporation
America (RCA) method. Then the wafers were rinsed in distilled water and then dried.
226 S. Rajamanickam et al.

The wafers were then deposited with ZnO seed layer of thickness 70 nm using RF
sputtering machine at 150 W power and room temperature. After that, the wafers were
annealed in a furnace at 350°C for 30 min. The wafers are then taped to a cleaned
microscope glass slide and immersed in equimolar concentrations of zinc nitrate
hexahydrate and hexamethylenetetramine (HMT) of 0.04 M and stored in an air tight
glass bottle. The bottle is then placed inside a preheated water dispenser capable of
maintaining water temperature of 90°C for 3 h. After the hydrothermal growth reaction,
the bottle is taken out and the samples were rinsed with deionised water and gently dried
with nitrogen gas, later on annealed for another 30 min at 350°C. Two samples are
labelled (a) and (b), with sample (a) as the control sample and sample (b) to be deposited
with Ag NPs-carbon composite.
ENSON EN-06B8 conductive silver paste is obtained, deposited onto a drying dish
and left to evaporate. Once dried, the silver paste is dissolved in acetone and rinsed thrice
with acetone. The prepared solution is then subjected to ultrasonic cleaning treatment for
3 h to break up any small particles with the prepared solution appearing slightly grey.
This solution is then drop casted onto sample (b) and placed on a hotplate at 100°C to
evaporate the solvent. Samples (a) and (b) are then used in the fabrication of UV
photodetector device. The fabrication of the UV photodetector device was performed
using RF sputtering of aluminium (Al) electrodes onto the sample. Figure 1 shows the
schematic design of sample (a) and sample (b).
The surface morphology of the samples was studied using field emission scanning
electron microscopy (FESEM- FEI Nova Nano SEM 450). The FESEM will also be used
to obtain energy-dispersive X-Ray spectroscopy (EDX) for elemental analysis. The
surface roughness of the samples is determined using Atomic Force Microscopy (AFM)
(Dimension Edge, Bruker). Sample (a) was analysed using the standard X-Ray
Diffraction (XRD) (PANalytical X’Pert Pro MRD system) analysis procedure whereas
sample (b) was analysed using the grazing incidence X-Ray Diffraction (GIXRD)
((D8 DISCOVER, Bruker) method. The GIXRD method is chosen for sample (b) is due
to its higher sensitivity in analysing the encapsulation on the ZnO NRs. The reflectance
measurement is conducted using the Cary 5000 UV Vis spectrophotometer.
Photoluminescence (PL) spectra of the samples are obtained using the Raman &
Photoluminescence Spectroscopy System (Model: HR 800 UV). Current-voltage (I-V)
and current-time (I-T) setup characteristics were examined using the Keithley 2400
system setup.

Figure 1 Schematic design of sample (a) and sample (b) (see online version for colours)
 Encapsulation of Ag nanoparticle-carbon composite and enhancement 227

3 Results and discussion

Figure 2 shows the FESEM, AFM and EDX results of samples (a) and (b). The FESEM
top view image of sample (a) shows the ZnO nanorods closely packed whereas for
sample (b) Ag NPs-C composite particles are seen on the surface with sizes reaching
1 µm in diameter. For the cross section FESEM image it is shown in sample (b) that a
thin film of Ag NPs-C composite around 200 nm thick is shown coating the upper part of
the ZnO nanorods. The presence of Ag and C is shown by the EDX spectra for sample
(b). The root mean square (RMS) surface roughness of sample (b) is lower than sample
(a), a reduction from 58.15 nm to 50.10 nm because of the coating, resulting in the filling
up of the small gaps between the nanorods, resulting in a smoother surface.

Figure 2 (i) FESEM top view, (ii) FESEM cross section, (iii) 3D AFM image and (iv) EDX
spectra of samples (a) and (b) (see online version for colours)
228 S. Rajamanickam et al.

Figure 3 shows the normalised XRD spectra of samples (a) and (b). For sample (a), the
main peak of (002) and second order diffraction peak (004) is attributed to the vertical
plane (JCPDS Card No. 01-080-0074) of ZnO NRs, indicating the nanorods grow
perpendicular to the substrate and having high crystallinity [1,13]. Sample (b) also shows
the main peak of ZnO (002) but with three additional peaks that is attributed to the Ag
NPs present in the encapsulation; the (111), (200) and (220) peaks. All peaks related to
Ag NPs in the XRD spectra can be inferenced as the NPs having face centred cubic
(FCC) structure from the database (JCPDS Card No. 4-0783) [14].

Figure 3 Normalised XRD spectra of samples (a) and (b) (see online version for colours)

Figure 4 PL spectra (i) and (ii), enlarged PL spectra (iii) and DRS of samples (a) and (b) (iv)
(see online version for colours)
 Encapsulation of Ag nanoparticle-carbon composite and enhancement 229

Figure 4 shows the PL spectra and diffuse reflectance spectra (DRS) for samples (a) and
(b). From the PL spectra, the ZnO NRs from both samples exhibited high near
band-edge emission (NBE) with a peak of 378 nm due to excitonic recombination and a
broad peak from 500 nm to 700 nm which is from the deep level emission (DLE) due to
ZnO defects in the NRs [2]. When the PL spectra is enlarged as shown in (ii), sample (b)
shows a broader peak for the NBE than sample (a). The full width at half maximum
(FWHM) for sample (a) is 10.99 nm and for sample (b) is slightly larger, at 11.89 nm. As
noted by other researchers, a larger value of the FWHM shows that there is an increase in
the impurity concentration in the ZnO NRs [15], which is caused by the addition of Ag
NPs-C particles. The DRS for both samples are shown in (iii). The strong absorption at
about 380 nm for both samples is due to ZnO direct band gap transition [16]. Between the
320–380 nm range, sample (b) shows higher reflectance than sample (a) which appears
that the Ag NPs-C composite reflects some emissions within that range. Another smaller
absorption at 320 nm is attributed to the silver plasmon resonance effect [17], proving the
presence of silver nanoparticles in sample (b).
The current-voltage (I-V) characteristics under dark (Idark) and light (Iphoto)
(illuminated at 395 nm and 460 nm) in addition to current-time (I-t) graph under pulsed
illumination (395 nm and 460 nm respectively) of samples (a) and (b) are presented in
Figure 5. Table 1 presents the dark and light current values taken at +5 V applied bias
along with the calculated responsivity and sensitivity values for both wavelengths. It was
observed that the current values detected in the I-t graph are higher than recorded in the
I-V curve. A possible explanation is given as follows: the I-V test undertaken lasts a few
seconds for each test, whereas the I-t test takes 2–3 min each test. This results in both
samples being subjected to longer illumination periods, resulting in larger electron-hole
pair generation and thus a higher current reading. The responsivity is the ratio of output
current to the light power illuminated onto the active surface of the photodiode. The
active surface area of the photodiodes is 0.16 cm2. The sensitivity is the percentage of the
ratio of light current to dark current at a given voltage bias. Sample (a) has the highest
responsivity under 395 nm illumination at 0.175 A/W. Sample (b) has significantly lower
responsivity under both wavelength illuminations as the Ag NPs-C composite coating the
ZnO NRs prevented some photons reaching the ZnO NRs. Upon addition of Ag NPs-C
composite, it resulted in some reflectance of UV rays from the surface of sample (b)
which is shown in the DRS from Figure 4. UV rays also could have been absorbed by the
carbon in the acrylic adhesive with similar mechanism by organic UV filter [18]. Sample
(a) shows slight responsivity in visible wavelength (460 nm) due to defects in the ZnO
NRs structure; possibly oxygen energy levels are introduced in the energy band of ZnO,
enabling ZnO to function as both UV and visible light photodetector [19]. However, for
sample (b), when Ag NPs-C composite is deposited onto the ZnO NRs, the carbon atoms
from the acrylic adhesive diffused into the ZnO lattice structure, creating new energy
states inside the wide band gap of ZnO, allowing it to be sensitive to visible light as
proposed by Xianbin Liu et al. [12]. The new energy states created in sample (b) are
much more in numbers than just the energy states due to ZnO defects in sample (a),
therefore sample (b) become more sensitive to the 460 nm illumination compared to
sample (a), as shown in (ii) and (iv) in Figure 5. Sample (a) shows a sensitivity of 8.85%
under 460 nm illumination while sample (b) shows a 262.16% sensitivity although at a
significantly lower responsivity of 0.005 A/W. Despite this setback in responsivity for
sample (b), sample (b) has potential to improve its responsivity by adding an amplifier
due to its high sensitivity of the 460 nm wavelength.
230 S. Rajamanickam et al.

Figure 5 I-V characteristics of samples (a) and (b) in the dark and illuminated under (i) 395 nm
and (ii) 460 nm wavelength, I-t graph for samples (a) and (b) illuminated under pulsed
(iii) 395 nm and (iv) 460 nm wavelength respectively (see online version for colours)

Table 1 I–V measurements on photodiode in dark and under illumination, responsivity, and
sensitivity at 395 nm and 460 nm of samples (a) and (b)

Sample Wavelength (nm) Idark (µA) Iphoto (µA) Responsivity (A/W) Sensitivity (%)
(a) 395 13.68 37.66 0.175 175.30
460 17.85 19.43 0.077 8.85
(b) 395 6.48 7.27 0.034 12.19
460 0.37 1.34 0.005 262.16

4 Conclusions

This paper investigates the effect of depositing Ag NPs-C composite on ZnO NRs and its
morphological, optical and electrical properties. FESEM imaging shows a thin layer of
Ag NPs-C composite encapsulating the top part of ZnO NRs, with EDX spectra showing
peaks of Ag and C. PL spectra show slight broadening and red shift of ZnO NBE peak at
378 nm. DRS of ZnO NRs encapsulated with Ag NPs-C composite shows higher
reflectance in the wavelength range (320–380 nm) which is in the UV range, indicating
the composite reflects wavelength in that range. n-ZnO/p-Si photodiode that is
encapsulated with Ag NPs-C composite shows higher sensitivity for visible wavelength
(460 nm) than without encapsulation, albeit with reduced sensitivity to UV wavelength
(395 nm).
 Encapsulation of Ag nanoparticle-carbon composite and enhancement 231

Acknowledgements

This work was supported by the Institute of Nano Optoelectronics Research and
Technology (INOR), Universiti Sains Malaysia (USM) and Nano-Optoelectronics
Research & Technology Laboratory (NOR Lab), School of Physics, Universiti Sains
Malaysia (USM). Our gratitude also goes to the Research Creativity and Management
Office (RCMO), USM, Malaysia, and the sponsor of Nippon Sheet Glass Foundation for
Materials Science and Engineering (NSG Foundation), Japan, for supporting under code
number of (304/CINOR/6501147).

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