J Mater Sci: Mater Electron

DOI 10.1007/s10854-016-4975-6

Investigation of structural, optical, magnetic properties

and antibacterial activity of Ni-doped zinc oxide nanoparticles
S. B. Rana1 • R. P. P. Singh2

Received: 28 February 2016 / Accepted: 9 May 2016

Ó Springer Science+Business Media New York 2016

Abstract In this study, pure ZnO and Ni doped ZnO exhibit considerable changes in the M–H loop, specifically
nanoparticles were successfully synthesized by using the the diamagnetic response changed into ferromagnetic
wet chemical precipitation method. Pure and Ni doped ZnO character for Ni doped samples in VSM investigation. The
nanoparticles samples were characterized by X-ray antibacterial activities of the Nickel doped zinc oxide were
diffraction (XRD), scanning electron microscopy (SEM), studied against Gram-negative (Shigella dysenteriae, Vib-
X-ray energy dispersive spectroscopy (EDS), UV–visible rio cholerae, and E. coli) via using agar well diffusion
(UV–Vis) and FTIR spectroscopy. The XRD investigation technique. Further, these Ni doped nanoparticles were then
of pure and Ni-doped ZnO nanoparticles samples reveal applied as antibacterial agent to control the microorgan-
and confirm the formation of single phase hexagonal isms or bacterial growth. Ni-doping on zinc oxide and
wurtzite structure, without formation of any secondary and exposure of sunlight enhanced the antibacterial activity
other impurity phases. XRD results further reveals the against bacterial pathogens which isolate at 40–45 lg
shifting of characteristics peak toward higher 2h (theta) concentration. Interestingly in this study, most effective
angle with Ni doping. This shifting of the XRD peaks antibacterial results were obtained against the water related
toward higher angle clearly indicates that Ni ions are bacteria such as E. coli and V. cholerae for Ni-doped ZnO
effectively incorporated in the ZnO lattice. Surface mor- NPs.
phology of pure and Ni doped ZnO nanoparticles samples
was performed by using the SEM confirms the formation of
spherical nanocrystallites with fine and clear defined 1 Introduction
boundaries. EDS spectroscopy indicates the substitution of
dopant Ni2? effectively in lattice site of Zn2? as evident Compound semiconductor nanocrystals have interested
from XRD result also. The carriers i.e. donors confined on different researchers because of their unusual and
the Ni sites were confirmed from the micro Raman spec- remarkable properties [1, 2]. In this category, Zinc oxide
troscopy. Optical property of Ni-doped samples is con- nanoparticles (ZnO) have been studied extensively from
firmed by using the UV–Vis absorption which showed blue last few decades due to their potential exceptional appli-
shift in absorption edge as compared to undoped ZnO cations in the field of optoelectronics due to its wide band-
nanoparticles. Undoped and Ni-doped ZnO nanoparticles gap (*3.37 eV) and high exciton binding energy
(60 meV) [3–5]. Recently, scientists and researchers are
investigating the effect of doping ZnO nanoparticles with
& S. B. Rana the transition metals such as Co, Fe and Mn. [6–10, 29].
shashi_rana12@yahoo.co.in Different theories have revealed that on doping ZnO
1 nanoparticles with these transition elements results
Department of Electronics and Communication Engineering,
Guru Nanak Dev University, Regional Campus, Gurdaspur, remarkable change in their different luminescent and
Punjab, India magnetic properties. Further, the transition metal doped
2
Department of Electronics and Communication Engineering, Zinc oxide semiconductors with room temperature ferro-
Arni University, Indora, H.P., India magnetism (RTFM) have been investigated for its

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advanced applications in the field of spintronics, where the oxygen species (ROS) on the surface of the nanoparticles
effort was made to find the means and ways for effective in the presence of light which further causes oxidative
utilization of these nanoparticles in both data storage and stress in bacterial cells. This phenomenon ultimately results
information processing [10–13]. In recent investigations, in the death of the cells or micro-organisms [27–32].
dilute magnetic semiconductor (DMSs) are formed by Satumal et al. [33] suggested and reported that decrease in
making the substitution of the cations on the host semi- ZnO nanoparticles size with the increased presence of TM
conductors material with small trace (doping) of the tran- doping element (Ag and Ni) can be attributed to better
sition metal (TM) ions [14]. Transition metal doped solubility of dopant element on the surface of the
semiconductors have attracted a lot of attention due to their nanoparticles. Thus, addition of Nickel in ZnO nanoparti-
significant applications such as short wavelength lasers, cles may result in varied particles size and hence may
UV detectors, field-effect transistors, non linear varistors affect its antibacterial activity.
and high sensitive chemical sensors. These transition Prime focus of this study is just to ensure how these Ni-
metals doping in semiconductor ZnO nanoparticles facili- doped ZnO nanoparticles can be recommended as a prob-
tates the generation of carrier induced ferromagnetism. In able water decontamination agent to protect water against
order to understand the underline mechanism in all these the bacterial pathogens. So, Ni-doped ZnO nanoparticles
processes, it is absolutely essential to synthesize the ZnO were considered in this research paper to explore their
based ferromagnetic material, where their physical and effectiveness as a prospective candidate for biological
structural properties must be well understood explicitly. applications, mainly as an antibacterial agent.
Experimental studies confirmed and revealed that the fer- In this paper, the effect of Ni doping on the structural,
romagnetism (FM) strongly depends on synthesis methods morphological, elemental, optical and magnetic properties
and environmental conditions used for the synthesis of the on ZnO nanoparticles were investigated by using XRD,
samples. Numerous researchers addressed room tempera- SEM, EDS, UV–Vis and VSM study respectively. It was
ture ferromagnetic behavior of transition metals (such as evident that by incorporating the Ni doping of ZnO
Co, Mn, Fe and Cr) doped zinc oxide nanoparticles [15– nanoparticles not only results in increase in ferromagnetic
17]. Among all these magnetic-metals, nickel is one of the properties in host semiconductor material but changes the
key dopant to achieve Curie temperature (Tc) above the lattice constant values in structural studies and changes the
room temperature. Some researchers observed the param- optical properties as well. These investigations were then
agnetic and ferromagnetic nature in ZnO at RT with dif- followed by study of antibacterial activity of doped ZnO
ferent composition of Ni content. Since the dilute magnetic nanoparticles against harmful bacteria pathogens.
semiconductor (DMS) contain a fraction of transition ele- Organization related to this research paper is summa-
ments, thermal stability of the doped metal ions, which rized as follows: Sect. 2, illustrate and explain the experi-
decide the material physical properties, are very essential mental procedure followed to synthesize the doped and
for practical applications. pure (undoped) ZnO nanoparticles, followed by experi-
Several chemical methods have been developed to mental procedure to measure the antibacterial activity of
synthesize the nanoparticles (NPs) of various materials of pure and Ni-doped ZnO. Thereafter, necessary instrumen-
interest. However, various chemical methods were used to tation used to characterize the structural, optical, FTIR and
prepare the ZnO based DMS materials, such as sol–gel magnetic properties of undoped and doped ZnO sample
method, hydrothermal, solvo-thermal, spray pyrolysis, co- was highlighted. In Sect. 3, different results have been
precipitation method etc. [18–23]. The sol–gel technique is discussed in detail related to above mentioned properties,
extensively used for the synthesis of novel ceramics whereas the Sect. 4 concludes the paper.
material and for the preparation of crystalline material ores
for metallurgical treatment. Among all these techniques,
wet co-precipitation method has been extensively adopted 2 Experimental method
to synthesis ZnO nanoparticles due to its economical (low)
cost rate, offers larger degree of solubility of dopants and 2.1 Synthesis of pure and Ni-doped ZnO
due to large yield of ZnO nanoparticles involved in the nanoparticles
process [24–26].
Apart from this, Zinc oxide nanoparticles find many All chemicals used in research work were procured from
potential applications in various chemical and biological Sigma-Aldrich with purity level of 99.99 % and used
fields, including antibacterial agent and in bio labeling. without any other purification. In order to synthesize pure
ZnO NPS have revealed and shown good bacterial growth ZnO nanoparticles, zinc acetate hydrated [Zn (CH3
inhibiting character. The antibacterial activity of a material COO)22H2O] (500 mg, 2, 0 mmol) was dissolved in dis-
mainly depends on the production or generation of reactive tilled water and stirred for 1 h. Next, a sodium hydroxide

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(NaOH) solution was added slowly in a drop-wise fashion Bruker AXS D8, Germany) which is equipped with gra-
to the mixture solution to maintain the pH * 10. The phite monochromator and a mirror fixed at the incidence
solution mixture was then stirred at room temperature for angle of 1°–5°. In this set up, we were using CuKa
about 3 h followed by aging for 24 h at the identical (Wavelength = 1.540 Å, 40 kV, 100 mA) as the radiation
temperature. After this step, white precipitates that formed source. The angular accuracy of this setup was fixed at
were then centrifuged, filtered and washed several times 0.001° and the angular resolution was kept about 0.01°.
(distilled water) and were finally annealed at 500 °C for The samples were scanned in angular direction which
2 h. In order to synthesize Ni-doped ZnO nanocrystals, varies from 20° to 90° (2-theta) with step size of 0.01°.
nickel acetate [Ni (CH3COO)22H2O] was mixed with Zinc Surface morphology or structural properties of pure and
Acetate solution in accordance with the calculated stoi- doped synthesized samples was ascertained and estimated
chiometric ratio. The required quantity of aqueous NaOH by using scanning electron microscope Carl Zeiss Supras
solution was then added drop by drop to the mixture 55 which operates at a high accelerated voltage of 15 kV.
solution to get (pH * 10). The method for the precipita- In order to investigate the optical properties of samples, the
tion of undoped ZnO nanoparticles was followed for the UV absorption spectra of these samples were recorded on
synthesis of Ni doped ZnO NPs. the double beam spectrophotometer (Systronics-2205)
having bandwidth of 1 nm and wavelength ranges from
2.2 Determination of antimicrobial activity 300 to 800 nm. Elemental composition of various sample
were ascertained by using EDS spectroscopy at an accel-
Antimicrobial activities of the synthesized pure ZnO and eration voltage of 200 keV. Raman spectroscopic investi-
Ni doped ZnO NPs were performed against three pathogens gation was performed by the using imaging spectrograph
namely Gram-negative (Shigella dysenteriae, Salmonella which consists of 400 mm focal length laser Raman
typhi and E. coli). The antibacterial activity of pure ZnO spectrometer (SEKI). The presence of various functional
and Ni-doped ZnO was performed by using nanoparticles groups was ascertained by using Fourier transform infra red
diffusion method [34]. Particular cultures of microorgan- (FTIR) spectroscopy using Thermo Nicolet 390 with KBr
isms were created on nutrient broth at 35 °C by shaking the pellet technique at room temperature in the range
incubator at 200 rpm. Each and every isolated bacterial 400–4000 cm-1. Magnetic hysteresis (M–H) loop at room
culture was homogeneously spread on the plates with the temperature (RT) was measured by using the Vibrating
help of sterile spreader. Bacterial culture lawn on nutrient Sample Magnetometer (VSM, Microsense EZ8) having
agar plate was arranged by spreading the 150 ll liquid maximum magnetic field strength of 22.6 kOe.
culture. Agar plates were kept in the standing position for
about 20 min, so that the culture gets absorbed. The 9 mm
size wells were then inserted into the agar by the use of 3 Results and discussions
head sterile micropipette tips. Each well is then sealed from
the bottom by 10 ll of molten agar in order to avoid the In this study, one of our aims was to highlight the various
leakage of loaded sample onto the surface of petri plate. results obtained by using different investigation techniques
After this step, nanomaterial’s (doped ZnO) suspension in for Ni-doped ZnO nanoparticles, but for comparison sake
the distilled water (60 llg/100 ll) was poured into each we included the results obtained for undoped ZnO
well of plate. Under the controlled incubation condition for nanoparticles. This has enabled us to compare the various
about 35 degree centigrade for the 24 h it results in for- structural, optical, magnetic and antibacterial activities of
mation of zone of inhibition in form of bacterial growth undoped and Ni-doped ZnO nanoparticles.
retardation which were then subsequently measured. In this
set up, distilled water was used to provide the blank control 3.1 XRD analysis of undoped and Ni-doped ZnO
and tetracycline is used as a positive control. After this nanoparticles
another set of nanomaterial loaded well plate was prepared
and exposed for 2 h in sunlight under the incubated opti- In this study, we compared the synthesized undoped ZnO
mum temperature. nanoparticles crystallite size with that of Ni doped ZnO by
using XRD technique. Figure 1a, b shows X-ray diffraction
2.3 Characterization of pure and Ni-doped ZnO (XRD) patterns of the synthesized undoped (pure ZnO) and
samples Nickel doped (Zn0.95Ni0.05O) samples. Each XRD sample
exhibit the hexagonal wurtzite phase without any impuri-
To accurately investigate the structural properties of ties and secondary phase formation.
undoped and Ni-doped ZnO nanoparticles XRD was per- It is clearly from XRD pattern (spectra) that all the
formed by using the X-ray diffractometer (model no. characteristic diffraction peaks can be indexed to the

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introduction of Ni dopant atom in host ZnO matrix. Hence,

we conclude that small change in 2-theta values of
diffraction peaks and broadening of peak are due to the
increase in micro-strain and the line broadening effect is
mainly caused by the size and micro-strain of doped ZnO
nanoparticles. Doped ZnO NPs size reduction is significant
as compared to undoped NPs and highlighted in Table 1.
Figure 1c clearly shows the shifting of characteristics
peak toward higher 2h (theta) angle value with Ni doping.
This shifting of the peak positions clearly indicates that Ni
ions are completely diffused (incorporated) in the Zn
position in the ZnO lattice [36].
However, the average crystallite size can be deduced
and calculated by using Scherrer’s Eq. (1) and was calcu-
lated to be in the range of 41–45 nm for doped to undoped
ZnO NPS and highlighted in Table 1.
kk
s¼ ð1Þ
bcosh
In above equation, s is grain size, b is the full width at half
maxima, k is the wavelength of X-ray used (1.547 Å) and h
is the angle of diffraction. Table 1 clearly showed that
lattice strain and dislocation density increases with the
doping of Ni ion as compared with undoped NPs as high-
Fig. 1 XRD spectra of a pure and b Ni-doped ZnO nanoparticles,
lighted in Table 1. From the d spacing values, lattice
c shifting of (101) peak toward higher angle for Ni-doped ZnO NPs constant ‘a’ and ‘c’ can be calculated by using the Eq. (2)
and their values are shown in Table 1.
 
diffractions of (100), (002), (101), (102), (110), (103), 1 4 h2 þ hk þ k2 l2
¼ þ ð2Þ
(200), (112), (201), (004) and (202) planes with the clear d2 3 a2 c2
hexagonal wurtzite structure [35]. These diffraction peaks
The ionic radius value for doped element Ni2? is 69 pm
are in close agreement with the standard value of JCPDS
and for Zn2? its value is 74 pm. It is clearly observed from
card no. 01-079-2206 card. From the XRD pattern of
the Table 1 that value of lattice parameters and d value
Fig. 1a, b it is clear that the Ni-doped samples shows
goes on reducing due to the smaller ionic radius of Ni ions
lowering of intensity peak as compared to undoped (pure)
due the substitution of Zn2? by Ni2? during the doping
ZnO NPs. This lowering of intensity of diffraction peaks of
process.
Ni-doped sample signifies that the crystalline character of
the ZnO NPs had reduced considerably due to Ni doping.
Further, we observe that the characteristic peak of (101) 3.2 Scanning electron microscope (SEM) analysis
plane related to doped sample shift toward the higher angle
as compared to undoped (pure) ZnO NPs as shown in The surface morphology of pure and Ni-doped samples was
Fig. 1c and illustrated in the subsequent discussion. Apart carried by using the scanning electron microscopy (SEM)
from this phenomenon, we also observe the broadening of investigation. Figure 2a, b shows the SEM images of pure
XRD peak of Ni-doped samples reveals that size of doped and Zn0.95Ni0.05O nanoparticles samples with an average
ZnO nanoparticles is smaller than the undoped ZnO NPs. particle size of around 65 and 60 nm respectively. The
The decrease in the crystallite size is chiefly due to the SEM micrograph of pure ZnO nanoparticles sample
distortion in a host ZnO lattice by the introduction of revealed that these nano particles are spherical in shape
impurities and the presence of Ni2? reduces the nucleation with large aggregation. It is clearly evident from the
and consequent growth rate of ZnO NPs. Close examination Fig. 2b that aggregation is almost restricted in Ni-doped
of the XRD spectra further revealed that some XRD peaks ZnO NPs sample, and particles appears in uniform and
appearing in undoped ZnO NPs at higher angles disappear consistent shape with slightly constricted size distribution.
in the Ni doped ZnO samples. This is due to the reduction of The nanoparticle size calculated from XRD spectra is rel-
grain size and presence of strain in the ZnO lattice due to atively different from the SEM micrograph measurement

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Table 1 Nanostructural properties of pure ZnO and Ni-doped ZnO nanoparticles

Sample Particle size (nm) Lattice strain Dislocation d101 (Å) Lattice constant
density 9 10-14 line2/m2
a c

Pure ZnO 45 0.0027 4.92 2.4767 3.234 5.281

Ni-doped ZnO 41 0.0030 5.67 2.4754 3.233 5.279

Fig. 2 SEM images of a pure ZnO, b Ni doped ZnO nanoparticles

because in SEM, computation related to size of particles

are performed by taking the difference of clear (noticeable)
grain boundaries, but the XRD measurements are taken
from the crystalline surface area which diffracts the X-ray
waves reasonably or effectively [37].
From Fig. 2b, it is clear that doped nanoparticles size
goes on decreasing because dopant Ni2? is diffusing evenly
or homogenously in the different sites and are noticeably
visible with less porosity in the background environment
(portion). Hence, it is clear from SEM micrograph that pure
ZnO NPs appears in bigger form, while doped (Zn0.95
Ni0.05O) nanoparticles appears in smaller size which veri-
fies our XRD results.
Elemental composition of the synthesized ZnO
Fig. 3 EDS spectra of Ni doped ZnO nanoparticles
nanoparticles (doped and undoped) was determined from
the energy dispersive X-ray spectroscopy (EDS) as shown
in Fig. 3. The EDS analysis confirms the presence of Ni, O reveals that Ni doped ZnO NPs were successful synthe-
and Zn in the doped sample with no presence of any other sized by the wet chemical precipitation method.
impurity element or phase. Figure 3 shows the EDS spectra
of Ni-doped ZnO NPs sample. 3.3 Optical absorption study
The EDS spectrum indicates that the synthesized Ni-
doped ZnO sample mainly contain Zn, Ni and O elements. Optical properties of undoped ZnO NPs become increas-
The EDS spectral peaks of O appeared at 0.5 keV, Zn ingly more and more prominent when size of particle is
appeared at 1, 8.5 and 9.6 keV respectively. Result of EDS reduced in nanoscale. Optical properties of pure ZnO and
spectra further confirm and verify the XRD result, which Ni-doped ZnO NPs were successfully investigated by

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employing UV–visible absorption spectroscopy. The band This phenomenon of increase in band gap energy (Eg)
gap of these compound semiconductor nanoparticles varies and absorption at the lesser wavelength can also be
as the different dopants can cause (create) different crystal explained on the basis of quantum confinement effect
defect in the ZnO crystal structure. The UV–visible amongst the individual doped ZnO nanoparticles.
absorption investigation of pure ZnO and Ni-doped ZnO
nanoparticles is shown in Fig. 4 in the wavelength ranges 3.4 FTIR study of pure (undoped) and Ni doped
from 300 to 800 nm. Absorbance value is exclusively ZnO nanoparticles
dependent on the various factors like size of nanoparticles
and deformities or defects in grain structure. The UV–Vis An FTIR spectrum was used to give the information about
spectrum of undoped ZnO NPs shows the edge absorption the chemisorbed species, elemental constituent of material
peak at 390 nm due to exciton recombination at room and presence of various functional groups in the material. It
temperature [38]. As the Ni doping concentration is also gives the information related to presence of outgoing
changed from pure ZnO the absorption edge is start to shift and incoming species that may exist on the surface of
towards lower wavelengths (blue shift) which further imply material. Various series of the peak ranges from 400 to
that the band gap (Eg) increases, which will be due to strain 4000 cm-1 are found to be present in FTIR spectra, which
or defects. All these factors leads to the reduction of show the existence of various functional groups and che-
crystallite size of Ni doped ZnO sample, which further misorbed species in undoped and doped ZnO. Apart from
verifies our result of XRD spectra. Figure 4, shows the this, FTIR spectroscopic investigation revealed the vibra-
absorption spectra of the pure ZnO and Ni doped ZnO tional frequencies of undoped (pure) ZnO and doped ZnO
nanoparticles with the absorption peak at 390, 387 nm nanoparticles. The FTIR spectra for pure and doped ZnO
respectively. NPs are shown in Fig. 5.
Table 2, summarizes the band gap energy (Eg = hc/k) The presence of absorption peak between 3025 and
value for undoped (pure) and Ni-doped ZnO nanoparticles. 3655 cm-1 corresponds to the vibration mode of O–H
The optical band gap value calculated in our pure ZnO group [40]. The absorption peaks observed at the value of
sample is small (3.19 eV) as compared with standard band 3458 cm-1 are due to the presence of O–H stretching of
gap value of bulk ZnO material i.e. 3.3 eV. But, the surface absorbed H2O molecules in Ni-doped and undoped
observed Eg value is in good agreement with the Eg value sample. The peaks found at 2855 and 2955 cm-1 are due to
highlighted in literature [39]. The increase in band gap the symmetric and asymmetric nature of C–H group. The
energy with the increase of Ni content is attributed to the absorption peak found at 2340 cm-1 was due to the exis-
incorporation of Ni2? ions into the ZnO host lattice. tence of CO2 molecules in the air [22]. Presence of the
weak absorption band found around 870 cm-1 was due to
the Ni–O vibrational frequency due to the presence of
Nickel in the ZnO lattice structure [41]. In case of undoped
ZnO, the absorption band of Zn–O stretching was found at
577 cm-1. Presence of peak at 502 cm-1 for Ni doped ZnO
nanoparticles will be attributed due to the inclusion of Ni2?
in ZnO host matrix. This peak was found to be absent in
FTIR spectra of pure ZnO NPs. The minor change found in
the observed values will be due to stretching of Zn–O–Ni
bond. When ZnO NPs samples are calcined above 500 °C,
various functional groups are removed from ZnO
nanoparticles surface easily. Observations related to FTIR
spectroscopy are found to be in good agreement with XRD
results as discussed earlier.

3.5 VSM study of pure and doped ZnO

nanoparticles

Magnetization measurements related to pure and Ni-doped

ZnO nanoparticles were carried out by using the vibrating
sample magnetometer (VSM) which uses the magnetic
Fig. 4 UV–visible absorption spectra of Pure ZnO and Ni doped ZnO hysteresis (M–H) curve. In this set up all the measurements
nanoparticles were carried out at the room temperature. Synthesized pure

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Table 2 Band gap energy (Eg)

Sample Absorption wavelength (k) (nm) Band gap energy (Eg = hc/k) (eV)
variation of pure ZnO versus
Ni-doped ZnO nanoparticles Pure ZnO 390 3.19
Ni doped ZnO 386 3.23

ZnO NPs sample clearly shows the diamagnetic behavior

(property) as shown in Fig. 5a. Diamagnetic behavior
(nature) of pure ZnO NPs has been reported in literature
[42].
From the magnetic hysteresis loops or M–H curve of
Fig. 6b it is clear that the Ni-doped sample show the fer-
romagnetic behavior at room temperature (RT). Table 3,
shows the value of magnetization saturation (Ms) and
remanent (Mr) in case of Ni-doped ZnO sample due to
ferromagnetic nature of Ni-doped sample. Various
assumptions associated with exhibition of room tempera-
ture ferromagnetism behavior have been addressed i.e.
secondary phase, clusters and ferromagnetism due to var-
ious defects in our following discussion.
Fig. 5 FTIR spectra of (a) undoped ZnO and (b) Ni-doped ZnO So far, different theories have been proposed regarding
nanoparticles
the origin of ferromagnetism this subject is still contro-
versial. One of hypothesis proposed that room temperature
(RT) ferromagnetism of Ni-doped samples is exhibited due
to different intrinsic and extrinsic phenomenon. Intrinsic
phenomenon’s normally occurs due exchange interaction
and extrinsic phenomenon occurs due to formation of
secondary phases and nanoclusters or secondary phases of
dopant (Ni) semiconductor atoms [43]. The linkage
between intrinsic defects such as Zinc or oxygen vacancies
and associated magnetism is also discussed in various
research papers. However, in our investigation, the XRD
and EDS spectra results clearly showed that dopant ions
(Ni) are effectively incorporated in the Zinc (Zn) wurtzite
lattice structure without formation of any metallic clusters
or secondary phases. Consequently, probability of ferro-
magnetism exhibition due to formation of secondary pha-
ses and metallic clusters is entirely ruled out in case of Ni-
doped sample.
Among other mechanism accountable for ferromag-
netism, the oxygen mediated exchange interaction among
the dopant ions (Ni) could be the probable mechanism
responsible for the observed ferromagnetic nature of the
Ni-doped samples. Das et al. [44], proposed that exchange
interaction mechanism mediated by the oxygen vacancies
(Ni–O–Ni) is mainly responsible for increase in magnetic
saturation when the dopant Ni is doped on the ZnO NPs, as

Table 3 Magnetization response measurement

Sample HC (Oe) Mr (emu/g) Ms (emu/g)
Fig. 6 M–H curve of a pure ZnO, b Ni-doped ZnO nanoparticles at Ni doped ZnO NPs 75 0.0026 0.023
room temperature

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process of doping increases carriers concentration in the vibrational mode associated with the Ni doping, which
form of oxygen vacancies. Increase in the value of satu- are bounded with the various donor defects. These var-
ration magnetization value at room temperature, is the best ious donor defects can be Zinc interstitials and doubly
possible mechanism for exhibition of room temperature oxygen vacancies defects which are the characteristic
ferromagnetism of Ni-doped sample. shallow donor defects in ZnO NPs.
From the analysis of XRD, EDS and VSM of our
samples, it is sensible to say that observed room temper- 3.7 Antibacterial activity of pure and doped ZnO
ature (RT) ferromagnetism is an intrinsic property of doped nanoparticles
material sample and not result due to formation of any
metallic clusters or secondary phases. In the present study, pure and Ni doped ZnO nanopar-
ticles were tested against three pathogens namely; S.
3.6 Raman spectroscopy of pure and doped ZnO dysenteriae, V. cholerae and E. coli using the nanopar-
nanoparticles ticles diffusion technique. Different researchers have
proposed that the antibacterial effectiveness of ZnO
Raman spectroscopy is considered as one of most versatile nanoparticles are generally depends on the presence of
method for detecting the incorporation of dopant and lattice reactive oxygen species (ROS), which is mostly resulted
defects in the host lattice structure [4, 45]. The surface of due to the larger surface area of NPs, release of Zn2? and
doped nanoparticles gets modified due to charge transport increase in oxygen vacancies. The hydroxyl radical,
between the dopant and host material, which results in superoxide and hydrogen peroxide related to the ROS
change of optical Raman spectrum [46]. group can cause appreciable harm to DNA and may lead
Figure 7 shows the Raman spectra of the doped and to death of cell [48]. In general, nanoparticles with
undoped ZnO NPs at room temperature in the range improved photocatalytic activity have smaller crystalline
100–700 cm-1. In case of undoped ZnO NPs, the strong size and large surface, which increases oxygen vacancies
and intense peak appearing at 435 cm-1 has been des- and resulting more reactive oxygen species ROS. The
ignated as high frequency branch for the E2 mode of presence of more number of reactive oxygen species
ZnO NPs. The different peaks appearing at 162, 333 and (ROS) is mainly resulted due to two main factors
575 cm-1 has been chosen as second-order vibration (a) diffusion capability of the different reactants (b) the
mode [2E2], the optical mode (transverse) with A1 formation of more and more oxygen vacancies. The
symmetry [A1] and the optical phonon mode (longitu- antibacterial activity of the ZnO nanoparticles is mainly
dinal) with E1 symmetry [E1] respectively [47]. The due to the oxygen vacancies which further depend on
blue shift in Raman spectra is observed and the corre- presence of Zn2? ions [49]. The increase of Nickel
sponding peak value is 540 cm -1 for Ni-doped ZnO NPs doping in ZnO nanoparticles can produce more number
samples. The Raman spectra of Ni-doped ZnO shows the of defects which were further verified and confirmed by
presence of large vibration mode centered around XRD results. Due to nickel doping the dislocation den-
532–540 cm-1 which can be chosen (assigned) as local sity and strain (which represent the defects) are found to
be increased as observed in XRD results.
Antibacterial activity of Ni-doped ZnO NPs can be
illustrated by using optical source of 600 nm wave-
length. By illuminating the sample with 600 nm light,
the defects in doped sample generate electron–hole pairs.
The holes split the water molecule (H2O) into (OH- and
H?) molecules from the ZnO NP’s suspension. Dis-
solved oxygen molecules present in solution are changed
into the superoxide anions (O2-), which sequentially
react with H? to produce (HO2) radicals, which upon
consequent collision with electrons that result in pro-
duction of hydrogen peroxide anions (H2O22-). This
hydrogen peroxide anion (H2O22-) then reacts with
hydrogen ions to produce the molecules of H2O2. The
generated molecule of H2O2 can infiltrate the cell
membrane and kills the microorganism or bacteria [50].
However, during the reaction the excess ROS is pro-
Fig. 7 Raman spectra of pure and doped ZnO nanoparticles duced, which can cause numerous sub cellular physical

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damage such as membrane, DNA damage and protein

denaturation. In this work, the Nickel doped ZnO NPs
exhibit enhanced antibacterial activity than the undoped
ZnO NPs.
In our study, antimicrobial activity of pure ZnO
nanoparticles was highest against E. coli (17 ± 0.4) and
lowest against S. dysenteriae (12 ? 0.5) as highlighted in
Table 4.
However, for Ni-doped zinc oxide nanoparticles,
antibacterial activity was enhanced significantly (30, 25
and 23 %) against S. dysenteriae, V. cholerae and E. coli,
respectively. However, photo-catalytically exposure (2 h)
of ZnO nanomaterials showed enhancement of (22, 25, 29
and 27 %) activity against S. dysenteriae, S. typhi, V.
cholerae and E. coli, respectively. For undoped (pure) ZnO
nanoparticles growth inhibition rate was found to be
increased by exposure of sun light as compared to unex-
posed plate by 16, 7 and 5 % for S. dysenteriae, V. cho-
lerae and E. coli, respectively as highlighted in Table 4.
Furthermore, we compared the antibacterial growth pattern
for S. dysenteriae, V. cholerae and E. coli growth patterns
in the Ni-doped and undoped ZnO nanoparticles under the
exposure of sunlight (2 h). Growth of bacteria in the
sample (100 lg/ml) of pure and Ni-doped zinc oxide
nanoparticles were recorded in nutrient broth medium for
(a) S. dysenteriae (b) V. cholerae (c) E. coli depicted in
(Fig. 8).
Zhang et al. [51] have previously reported the ZnO
bactericidal property in E. coli, S. typhi, B. subtilis and S.
aureus. The unusual bactericidal behavior of ZnO and Ni-
doped ZnO might be due to chemical interactions between
nanomaterials and membrane proteins and formation of
free radicals in the presence of ZnO nanoparticles.
In nutshell, aim of this study is to investigate how
synthesized Ni-doped ZnO nanoparticles can be used as an
effective and strong antibacterial agent against three water
borne bacteria in presence and absence of sunlight. These
research finding encourage us to use Ni-doped ZnO
nanoparticles as a potential antibacterial agent in various
biological and pharmaceutical applications in future.

Table 4 Zone of inhibition for bacterial growth in pure and doped Fig. 8 Growth response or pattern of bacteria in pure and Ni-doped
ZnO nanoparticles without and with the exposure of sunlight Sample for three pathogens a S. dysenteriae, b V. cholerae, c E. coli

Treatment Diameter zone of inhibition (mm)

S. dysenteriae V. cholerae E. coli 4 Conclusions
Without sunlight exposure
In this research investigation, wet chemical synthesis of
Pure ZnO 12 ± 0.5 16 ± 0.5 17 ± 0.4
pure and nickel-doped ZnO nanoparticles were success-
Ni-doped ZnO 17 ± 1.2 21 ± 1.2 23 ± 1.5
fully achieved with clear wurtzite structure. XRD spectra
Exposure with sunlight (2 h) confirmed the incorporation of Ni2? ions into the lattice
Pure ZnO 16 ± 0.5 19 ± 0.5 20 ± 0.4 site of Zn2? ions in the host ZnO matrix. Spherical mor-
Ni-doped ZnO 19 ± 1.2 24 ± 1.2 25 ± 1.5 phology of pure and doped ZnO nanoparticles was

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 J Mater Sci: Mater Electron

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