Materials Science in Semiconductor Processing 122 (2021) 105485

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Materials Science in Semiconductor Processing

journal homepage: http://www.elsevier.com/locate/mssp

Rare earth metal co-doped Zn0⋅9La0.05M0.05O (M = Yb, Sm, Nd)

nanocrystals; energy gap tailoring, structural, photocatalytic and
antibacterial studies
Tauseef Munawar a, Muhammad Shahid Nadeem a, Faisal Mukhtar a, Murtaza Hasan b,
Khalid Mahmood c, M.I. Arshad c, Altaf Hussain a, Adnan Ali c, Muhammad Saqib Saif b,
Faisal Iqbal a, *
a
Department of Physics, The Islamia University of Bahawalpur, Bahawalpur, 63100, Pakistan
b
Department of Biochemistry & Biotechnology, The Islamia University of Bahawalpur, 63100, Pakistan
c
Department of Physics, Government College University Faisalabad, 38000, Pakistan

A R T I C L E I N F O A B S T R A C T

Keywords: Novel Zn0⋅95La0⋅05O and co-doped Zn0⋅9La0.05M0.05O (M = Yb, Nd, Sm) nanocrystals were prepared by co-
RE elements precipitation method. Different analytical techniques such as XRD, FTIR, SEM, and UV–vis were used to inves­
Antibacterial activity tigate the effect of doping of rare-earth (RE) ions in ZnO lattice. The microstructural study was performed using
Photocatalytic activity
Scherrer, W–H, and SSP methods. UV–vis analysis has shown that the energy bandgap is redshifted (3.2–2.8 eV)
Microstructural analysis
Optical properties
by rare-earth (RE) ions doping in ZnO. The other optical parameters were also investigated to strengthen the
Zinc oxide optical study. The photocatalytic performance of grown catalysts was tested under direct sunlight against
methylene blue (MB), rhodamine-B (RhB), and phenol (Ph). The antibacterial activity was carried out against
S. aureus and P. Vulgaris bacteria. The La/Sm co-doped nanocrystal has the highest photocatalytic and anti­
bacterial activity than others grown catalysts.

1. introduction conductivity, chemical stability, and low toxicity. It is a versatile n-type

In recent years, environmental pollution due to an increase in in­
dustrial activities commonly caused by organic pigments, textile,
carcinogenic dyes, and bleaching industries are the forefront challenge
for the research community to reduce harmful effects on public health
worldwide [1–3]. The use of harmful dyes has a diverse impact on
humans as well as aquatic ecologies. On the other hand, the appearance
of infectious diseases mainly causes by bacterial strains such as
P. Vulgaris, E. coli, S. typhi, S. flexneri, S. epidermis, P. aeruginosa,
S. aureus, and so on are the severe menace to public health throughout
the world. Recently, tremendous efforts have extensively been carried
out for the innovative research of photocatalytic and antimicrobials
applications [4]. The semiconductor solar photocatalysis technology has
attracted significant attention for the degradation of contaminants,
reduction of CO2, production of H2, and so forth [5,6]. Among different
metal oxides, ZnO possesses captivating antibacterial and photocatalytic
properties due to its eco-friendly characteristics, high biocompatibility,
semiconductor with high excitonic binding energy (60 meV) and a direct
wide energy bandgap (3.37 eV) [7,8]. ZnO has become a favorable
material for technological applications such as photodetectors, opto­
electronic devices, chemical sensors, and biological medicine [9].
Conversely, pure ZnO has some limitations also, including a wide
bandgap of 3.37 eV and the fast recombination rate of charge carriers,
causing lower photocatalytic performance [10–12]. To overcome these
snags, significant chemical alterations have been implemented, such as
structural design, doping, and co-doping [13], etc. In particular, the
co-doping in ZnO is a promising substitute approach that significantly
increases the surface defects and ostensibly broadens its absorption in
the visible range with improved quantum proficiency [14].
Rare earth (RE) doped metal oxides are among the interesting class of
materials that have attracted considerable attention due to practical
applications [15,16]. The improvement in the optical absorption, pho­
tocatalytic, antibacterial, and physical properties of ZnO by doping of
rare earth elements have been investigated by different research groups

* Corresponding author.
E-mail address: faisal.iqbal@iub.edu.pk (F. Iqbal).

https://doi.org/10.1016/j.mssp.2020.105485
Received 10 February 2020; Received in revised form 5 September 2020; Accepted 29 September 2020
Available online 14 October 2020
1369-8001/© 2020 Elsevier Ltd. All rights reserved.
T. Munawar et al.
[17,18]. Among the various available rare earth metals, lanthanum (La),
ytterbium (Yb), neodymium (Nd), and samarium (Sm) are the appro­
priate elements to enhance the physical properties of ZnO [19–23].
Several research groups have stated the effect of individual RE element
on different properties of ZnO [24–27], but there is scarce literature
available about La co-doped with Yb, Nd, and Sm in ZnO matrix. In this
context, the novel Zn0⋅95La0⋅05O and Zn0⋅9La0.05M0.05O (M = Yb, Nd, Sm)
nanocrystals were synthesized by co-precipitation method followed by
characterization with XRD, FTIR, UV–vis, and SEM. The detailed
microstructural study was carried out using Scherrer, W–H, and SSP
methods. The optical properties of synthesized nanocrystals were
investigated in detail. The photocatalytic performance of as-prepared
nanocrystals was studied under direct sunlight for photodegradation
of MB, RhB, and Ph, and the antibacterial performance was tested to­
wards G-positive Staphylococcus aureus and G-negative Proteus Vulgaris
bacterial strains.
2. Experimental procedure
2.1. Materials
Zinc acetate dihydrate (Zn(CH3COO)2⋅2H2O) was used as precursor
and nitrates of lanthanum (La(NO3)3⋅6H2O), ytterbium (Yb
(NO3)3⋅6H2O), neodymium (Nd(NO3)3⋅6H2O), and samarium (Sm
(NO3)3⋅6H2O) were used as a doping source and NaOH as a precipitation
agent. The methylene blue (MB), rhodamine-B (RhB), and phenol (Ph)
were used as an organic pollutant. All chemicals from Sigma Aldrich
were analytical grade and used as received.
2.2. Sample synthesis
For the synthesis of La-doped ZnO, the suitable amount of zinc ace­
tate dihydrate and nitrate salt of lanthanum were mixed in distilled
water. For co-doped nanocrystals, an appropriate amount of zinc acetate
dihydrate and nitrate salt of lanthanum together with Yb or Nd or Sm
salts were mixed separately and stirred for 30 min. Later, 0.1 M NaOH
solution was dropwise added into the above solution to achieve pH = 10.
The suspensions were stirred for 3 h at room temperature until pre­
cipitates formed. The obtained precipitates were washed, filtered, dried
at 100 ◦ C for 3 h, and annealed at 700 ◦ C. The synthesis process is
illustrated in Fig. 1.
2.3. Photocatalytic test
The photocatalytic activity of all grown nanocrystals/catalysts is
tested using MB, RhB, and Ph under direct sunlight. The photocatalytic
Fig. 1. Scheme representing the synthesis procedure of nanocrystals.
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Materials Science in Semiconductor Processing 122 (2021) 105485
test is carried out at Bahawalpur, Pakistan, Time: between 11:20 a.m. to
12:00 noon, dated: 17-Oct. 2019. The intensity of sunlight radiation lies
from 648.91 to 715.45 W/m2 measured by Kipp & Zonen CMP-11 pyr­
anometer. The experiment starts by taking 20 mg of grown catalysts and
mixed in 50 mL MB, RhB, Ph solutions in separate beakers, having a
concentration of 10 mg/L each. All other photocatalytic experiment
procedure is already discussed in the previous report [28]:
2.4. Antibacterial test
The antibacterial test was carried out against Staphylococcus aureus
and Proteus Vulgaris bacteria. Bacterial cultures are swabbed in nutrient
agar (6 g/200 mL) modified plates. The grown products are dissolved in
deionized water (15 mg/mL) and Whatmann filter paper cut in discs
form diameter 5 mm are immersed with the solution having concen­
trations 10, 20, and 30% and put on bacterial plates. The zone of inhi­
bition (ZOI) was measured after incubated overnight at 37 ◦ C.
2.5. Characterization
The characterization tools were already discussed in the previous
paper [29,30].
3. Results and discussion
3.1. X-ray diffraction
Fig. 2 (a) exhibits the XRD pattern of ZLa, ZLaYb, ZLaNd, and ZLaSm
nanocrystals. All the diffraction peaks with intensities are consistent
with ZnO hexagonal wurtzite structure (space group: P63mc, JCPDS card
No. 01-074-0534). As no characteristic peaks of impurity or secondary
phases such as RE oxides or Zn(OH)2 are detected, which confirmed that
obtained nanocrystals have single phase and dopant ions were success­
fully substituted/incorporated into ZnO matrix. The different physical
parameters are calculated using equations summarized in Table S1
(Supplementary data). From the calculation, it can be perceived that for
all co-doped ZnO nanocrystals, the value of lattice constant, volume of
the unit cell, and d-spacing values are larger than ZLa nanocrystal. This
variation may ascribe due to doping of RE ions (La3+, Yb3+, Nd3+ and
Sm3+) into the ZnO crystal lattice because the ionic radii of La3+ (1.16
Å), Yb3+ (0.86 Å), Nd3+ (0.98 Å) and Sm3+ (0.96 Å) are larger than Zn2+
(0.74 Å) ions [16,17,31]. The diffraction peaks of co-doped ZnO nano­
crystals shifted to a lower angle (Fig. 2(b)) that further approved suc­
cessful incorporation. Similar shifts were also reported by other research
groups [32]. It is observed that the APF increases for ZLaYb, ZLaNd, and
ZLaSm, as compared to ZLa nanocrystal. The volume of nanoparticles
T. Munawar et al.
Fig. 2. (a) XRD patterns of ZLa, ZLaYb, ZLaNd, and ZLaSm nanocrystals, (b) Peak shifting of (100), (002) and (101) plane, and (c) Texture coefficient (TC(hkl)) for
prominent peaks.
and the number of the unit cell have a similar kind of variation as
average crystallite size. The value of R is maximum (>1) for ZLaSm
nanocrystal as compared to others as lattice alteration prompted into the
ZnO matrix by dopant. The texture coefficient (TC(hkl)) is calculated
using the relation:
I(hkl) /Io (hkl)
TC(hkl) = ( ) / (1)
1
N
I(hkl) Io (hkl)
where I(hkl) = peaks intensity calculated from XRD, Io(hkl) = standard
intensity, and N = number of peaks. The variation of TC(hkl) with the
composition is presented in Fig. 2(c). As, TC(hkl) is higher than one for
the plane (002) (ZLa), (002) (101) (ZLaYb), (100) (101) (ZLaNd), and
(002) (ZLaSm), which indicate an increased number of grains along
these planes.
To support the XRD analysis, other structural parameters such as
positional parameter (μ), bond-length of the nearest neighbor along c-
axis (b), and the second-nearest neighbor distance b1’, b2’ and b3’, bond
angle α and β are also calculated [33]. The equations used and calculated
values are provided in Table S2.
3.1.1. Microstructural analysis
The crystallite size and micro-strain can significantly contribute to
altering the physical properties of nanocrystals and may cause broad­
ening of XRD diffraction peaks. The crystal imperfections (lattice
dislocation) are the primary cause of strain resulted from the doping of
different ionic radii RE ions. For a more accurate approximation of
various microstructural parameters, the Scherrer, W–H, and SSP
methods are used, and their detail is discussed in the previous report
[33], and plots are presented in Fig. 3(a–e). The calculated values of
average crystallite size and lattice strain are summarized in Table S3.
The results showed that crystallite size increased for all co-doped sam­
ples, and there is a tensile strain. The dislocation density ‘δ’ is calculated
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Materials Science in Semiconductor Processing 122 (2021) 105485
by δ = 1/D2, which measured the number of vacancies/defects in the
nanocrystals, indicated an opposite trend with crystallite size.
3.2. FTIR analysis
FTIR spectra of ZLa, ZLaYb, ZLaNd, and ZLaSm nanocrystals are
shown in Fig. 4(a). All absorption bands frequencies are provided in
Table S4. The bands at 500, 498, 496, and 496 cm-1 are the characteristic
Zn–O stretching bond vibrations of ZnO wurtzite lattice (Fig. 4(b)) [20,
34–36]. The prominent absorption bands at 563-698 cm-1 have resulted
in Zn-M-O (M = La, Yb, Nd, Sm) lattice vibrations [26]. Substitution of
La3+, Yb3+, Nd3+, and Sm3+ ions is further confirmed by this spectra.
The new absorption bands have appeared in co-doped samples endorsed
the incorporation of RE ions into ZnO lattice, as confirmed by XRD. The
alteration in the vibrational frequency from 500 to 496 cm-1 is due to the
disruption of Zn–O bonding and the change in bond lengths caused by
RE ions co-doping. The vibrational frequency, along with intensity
change around 563-698 cm-1, indicates a change in defect state density
adjoining to RE ions in Zn–O bonding.
Additional bands perceived around 839 cm-1 and 1133-1187 cm-1 are
due to C–OH and C–H vibrations [37,38]. The band at 1381–1394 cm-1
is due to NO-3 ions, indicates that the nitrate ions could not be removed
after washing [37]. The absorption band observed near 1561-1569 cm-1
is due to C–
– O stretching vibration [39]. The additional bands appeared
around 2360-2366 cm-1 are due to CO2 molecules that came from the air,
and the band at 2888 cm-1 is related to symmetric and asymmetric C–H
vibrations [40].
Additionally, to support the FTIR study, the wavenumber of the
Zn–O bond is estimated using bond length value from XRD. The relation
used to calculate wavenumber (υ), force constant (k), effective mass (μ),
optical phonon frequency (υo), and Debye temperature (θD) [30] along
with their calculated values are listed in Table S5. The wavenumber is
well-matched with XRD results.
T. Munawar et al. Materials Science in Semiconductor Processing 122 (2021) 105485

Fig. 3. (a) Scherrer plot, (b) W–H plot UDM, (c) W–H plot UDSM, (d) W–H plot UDEDM, and (e) SSP method to estimate microstructural parameters.

Fig. 4. (a) FTIR spectra of all grown nanocrystals in the wavenumber range from 450 to 4000 cm-1, and (b) The enlarged view in the wavenumber range from 450 to
1000 cm-1.

3.3. SEM analysis ZLaSm nanocrystal has a porous structure with high agglomeration.
Similar morphology of Sm-doped ZnO was also described by H⋅P
The surface morphology of all grown nanocrystals is presented in Nagaswarupa at al [41].
Fig. 5(a–d). The SEM images of ZLa, ZLaYb, ZLaNd, and ZLaSm nano­
crystals have not shown noticeable variations. The SEM micrographs
showed the agglomerated nanoparticles with porous morphologies. The

4
T. Munawar et al.
Fig. 5. SEM images of (a) ZLa, (b) ZLaYb, (c), ZLaNd, and (d) ZLaSm
nanocrystals.
3.4. Optical analysis
3.4.1. Absorption and transmission spectra
Fig. 6(a and b) exhibits the absorption and transmission spectra of
ZLa, ZLaYb, ZLaNd, and ZLaSm nanocrystals. The ZLa nanocrystal re­
veals an absorption band at about 384 nm in UV-region, and the addition
of Yb3+, Nd3+, and Sm3+ ions along with La3+ significantly increased
absorption in the visible region with absorption maxima located at 420,
402, 443 nm respectively. The absorption band gets redshifted
(384–443 nm) in all co-doped nanocrystals due to the generation of
lattice defects in ZnO. The transmittance in synthesized samples is also
increased in the visible range due to the variation in crystal disorder and
crystallite size effect. The existence of optical absorption edge and
higher transmission in the visible region for co-doped nanocrystals
shows that grown nanocrystals are suitable for photocatalytic activity in
both UV and visible regions.
3.4.2. Optical energy bandgap
The optical band gap (Eg) of grown products is calculated by
employing various methods [33], i.e., Tauc’s relation (Fig. 7(a–d)),
energy equation, first derivative method (Fig. 8(a)), and Vegard’s law.
The values of energy bandgap obtained from the different methods are
very close to each other (see Table 1). Furthermore, to confirm the
Fig. 6. Variation of (a) Absorbance, and (b) Transmittance with incident photon wavelength for all grown nanocrystals.
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Materials Science in Semiconductor Processing 122 (2021) 105485
optical band transition mode (n) whether the grown materials are direct
or indirect bandgap, the power factor (n) is calculated (Fig. 8(b)). The
calculated values of n of all the nanocrystals are given in Table 1, which
approximately equal 1/2 confirmed that the synthesized products are
direct bandgap materials. The VB and CB edge potentials (EVB and ECB)
(Fig. 7(e)) of grown nanocrystals at the zero point charge are computed
using equations discussed in the previous report [42]. The energy
bandgap values estimated from different methods for all co-doped
nanocrystals were decreased as compare to ZLa nanocrystal. The
observed redshift in energy bandgaps with RE (La3+, Yb3+, Nd3+, and
Sm3+) ions co-doping is generally due to three effects: increase crys­
talline size, the strong orbital coupling, and new impurity bands. First,
the increment in the crystallite size (see Table S3) causes a decrease in
the bandgap. Second, the co-doping may originate sp–d exchange
interaction among host electrons and the localized d-electrons of RE
ions. The exchange interactions (p− d, s− d) are causing a positive and a
negative revamping to the VB and the CB edge apart, causing the redshift
of energy bandgap. Third, the introduction of RE ions (impurities) in the
ZnO host lattice may introduce intermediate energy levels (electron
states) of impurity bands that lie adjacent to the lower edge of the
conduction band and generates the new lowermost unoccupied molec­
ular orbital, resulting in the reduction of the bandgap. Similar results of
bandgap shrinkage due to RE ions have been reported in the literature
[25,43]. Furthermore, the results demonstrated that co-doping played
an essential role in the alteration of the bandgap of ZnO and magnified
its visible light response, which is asserting for various potential appli­
cations. The Eg in the visible range propose that RE co-doped nano­
crystals can absorb UV–visible light of the sunlight, is the evidenced that
co-doped nanocrystals could be excellent sunlight or visible-light-driven
photocatalysts.
3.4.3. Urbach energy
The incorporation of dopant into semiconductor material often
causes band tailing, associated with localized states extended in the
conduction band or valence band originated from crystalline imperfec­
tion and compositional inhomogeneity. In the lower photon energy re­
gion, the spectral dependence of photon energy (hυ) and absorption
coefficient (α) is the so-called Urbach empirical rule [44], given as; α =
αo exp(hυ /Eu ), where Eu is the Urbach energy or band tail energy which
measures the degree of disorder or characterizes local defects and αo is a
constant. Taking the logarithm of the former equation, a straight line
equation is a form given as ln α = ln α + (hυ /Eu ). By plotting ln(α) on
the y-axis and photon energy (hυ) on the x-axis for all nanocrystals
(Fig. 8(c)) and linear fit the data, slope inverse equals to Eu and the
intercept equals to ln(αo). The measured values of αo and Eu are given in
Table 1. It is observed from the results that the Eu revealed an opposite
trend then Eg, which approved the relationship among these two factors.
This specifies that variation in the optical bandgap is associated with the
disorder disparity. As the Urbach energy is associated with lattice
T. Munawar et al.
Fig. 7. (a–d) Variation of (αhυ)2 with the photon energy and (e) Comparison of energy levels of ZLa, ZLaYb, ZLaNd, and ZLaSm nanocrystals.
structural disorder, it can be concluded that the incorporation of
different RE ions along with La3+ ion may cause to increase defects/­
disorder in ZnO lattice.
3.4.4. Refractive index (n)
The refractive index is an essential parameter in the research of
optical communication and designing optoelectronic devices. The
refractive index (no) can be calculated using the relation between energy
bandgap (Eg) and refractive index (no). In the present study, to calculate
no various relationships between Eg and no are used [33]. The calculated
values are listed in Table S6, which showed that the optical dielectric
constant ε∞ = n2. The calculated values by using different relations are
intercorrelated, as shown in Table S6. The small variation of refractive
index (no) is due to the different stoichiometry of co-doped nanocrystals
as well as the interaction of RE ions (La3+, Yb3+, Nd3+, and Sm3+) with
the host ZnO lattice.
3.4.5. Extinction coefficient (k)
The extinction coefficient or absorption index (k) is an essential
optical constant, expresses the fraction of light lost or attenuation of
light per unit distance in a material. The k can be determined using the
value of α and λ by using the following equation [45]: k = 4απλ . Fig. 9(a)
displays the spectral changes of k with λ for all nanocrystals. It is
observed that k is the maximum for ZLa in UV-region which show the
anomalous dispersion and for all co-doped nanocrystals in the visible
region show normal dispersion behavior. Ideally, for transparent
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Materials Science in Semiconductor Processing 122 (2021) 105485
material, the value of k in the visible region should be zero, but grown
nanocrystals are semi-transparent and have exhibited a low value for k
due to absorption of light at grain boundaries. This may be due to the
polycrystalline nature of nanocrystals or defects generate due to
different RE ions dopants. The observed attenuation in k values with
increasing wavelength values specified that optical loss reduced by
increasing incident wavelength. This implies that RE ions co-doped
nanocrystals are promising optical materials for long-wavelength or
visible regions.
3.4.6. Optical conductivity
The optical conductivity (σ opt) is a significant factor in understanding
the optical performance of the material. It measures the conductivity or
frequency response of the material with incident photons and strongly
depends on the optical energy bandgap. The optical conductivity (σ opt)
can be determined using relation [45]: σ opt = αnc/4πk, where, c, k, and
n are the velocity of light in free space or air, extinction coefficient, and
refractive index, respectively. Fig. 9(b) exhibits the change in optical
conductivity with the wavelength for all synthesized samples. The op­
tical conductivity increases and is maximum at the absorption point
(380–445 nm) then decreases for all nanocrystals. The variation of op­
tical conductivity is ascribed to the excitation of carriers (VC to CB) due
to light absorption in the band edge region equivalent to the bandgap of
grown nanocrystals. It can be perceived that the optical conductivity
varies with the accumulation of different RE ions and is higher for
ZLaSm nanocrystal. The maximum optical conductivity in the visible
T. Munawar et al. Materials Science in Semiconductor Processing 122 (2021) 105485

Fig. 8. (a) Plots of derivative of absorbance with respect to photon energy, (b) Illustration of ln (hυ-Eg) (eV) against ln (αhυ) (eV), and (c) The dependence of ln(α)
upon incident photon energy (hυ).

Table 1
The absorption edge, the value of optical bandgap calculated from different methods, transition power factor (n), Urbach energy (Eu) and constant (αo) for ZLa, ZLaYb,
ZLaNd, and ZLaSm nanocrystals.
Composition Absorption λ Eg (eV) Energy Eg (eV) Tauc’s Eg (eV) Derivative Eg (eV) Transition power Urbach energy The constant
(nm) equation relation method Vegard’s law factor (n) Eu (eV) (αo)

ZLa 384 3.229 3.223 3.234 3.254 0.499 0.973 10.336

ZLaYb 420 2.952 2.993 2.963 3.162 0.537 1.052 8.659
ZLaNd 402 3.085 3.018 3.098 3.199 0.518 0.678 2.890
ZLaSm 443 2.799 2.826 2.804 3.134 0.486 1.447 67.696

Fig. 9. Variation of (a) Extinction coefficient, and (b) Optical conductivity with incident photon wavelength for all grown nanocrystals.

region shows that all co-doped nanocrystals are excellent optical con­ 3.5. Photocatalytic activity
ducting materials, and the optical conductivity of ZnO can be modified
by RE ions co-doping. The photocatalytic activity of ZLa, ZLaYb, ZLaNd, and ZLaSm
nanocrystals was performed against MB, RhB, and Ph under sunlight

7
T. Munawar et al. Materials Science in Semiconductor Processing 122 (2021) 105485

illumination, and absorption spectra are shown in Fig. S1, S2 (a-c). It is band (VB) can snare on the surface of the catalyst and reacts with OH-
noteworthy to mention that MB, RhB, and Ph are degraded by all pre­ ions and H2O to generate OH* radicals. The hydroxyl (OH*) and su­
pared catalysts but higher for co-doped nanocrystals. The degradation peroxide (O2*-) radicals reacts with dyes molecules and decompose into
efficiency of all grown nanocrystals against MB, RhB, and Ph are given in intermediates compounds. The degradation mechanism is given below:
Table 2 and presented in Fig. 10(a–c). Remarkably, as-prepared catalysts
ZnO + hυ →ZnO (e− + h+ ) (2)
have the highest efficiency for MB than RhB, and Ph. The degradation of
MB, RhB, and Ph without catalysts are also tested (Fig. 10(d)) with no
RE3+ + e− →RE2+ (electron trapping) (3)
noticeable degradation observed. To investigate the kinetics of the
degradation reaction quantitatively, a pseudo-first-order kinetic model
RE2+ + O2 →RE3+ + O*−2 (electron transfer) (4)
is used discussed in the previous report [46–48] (Figs. S3(a–c)). This
evidenced that the photodegradation of dyes follows the first-order ki­
e− (ZnO) + O2 → O*−2 (5)
netics model. The calculated rate constant (k) and R-square values are
listed in Table 2. The rate constant (k) for MB degradation is higher as
e− (ZnO) + 2O2 + 2H + → H2 O2 + e− →OH * (6)
compared to RhB, and Ph.
The possible factors responsible for a remarkable enhancement in
h+ + H2 O→H + + OH * (7)
sunlight driven photocatalytic activity of RE metal ions co-doped ZnO
catalysts are following. First, intentional structural defects are generated
h+ + OH − →OH * (8)
in the ZnO matrix by doping RE metal ions cause the separation of
charges efficiently and increase the transfer rate of electrons to dissolve
Organic pollutants + OH * →Intermediates (9)
oxygen, which considerably improved the photocatalytic activity [49].
Tayade et al. [50] and Khanizadeh et al. [51] stated that inhabit of
Organic pollutants + O*−2 →Intermediates (10)
interstitial sites is more favorable in the photocatalytic reaction as
compared to substitutional positions. Here, RE ions La3+, Yb3+, Nd3+, Based on standard redox potentials of E o
) = -0.33 eV, OH* /
(O2 /O*2 −
and Sm3+ have significantly larger ionic radii than the host ZnO crystal H2 O = 2.27 eV, OH /OH = 1.99 eV, (Nd /Nd2+ ) = -0.40 eV,
* − 3+

lattice, so RE ions most probably have occupied interstitial positions and (Yb3+ /Yb2+ ) = -1.05 eV, (Sm3+ /Sm2+ ) = -1.55 eV and Ecb (ZnO) = -0.50
may cause charge imbalance (evidence from XRD). This charge disparity eV vs. NHE [54,55], a graphic model is suggested to demonstrate the
is reimbursed by hydroxyl groups and can lead to an amelioration of possible synergetic effect of RE ions on the photodegradation of MB and
surface hydroxyl groups, alternatively enhanced photocatalytic activity. RhB dyes is displayed in Fig. 11. It is important to mention that redox
Second, the co-doping may lead to enhance absorption in the visible potentials of Sm are more negative than others and laid above the CB
region and narrowing the bandgap (Fig. 6(a)) as compared to La-doped ZnO, resulted in an increase in electron trapping and greater photo­
ZnO (evidence from UV–vis) that is beneficial for excitation of more catalytic activity than Yb and Nd co-doped nanocrystals.
electrons from VB to CB. This decrement in energy bandgap also leads to
hindering the recombination of charge carriers due to the formation of 3.7. Antibacterial activities
new energy states [52]. The defects could act as trap centers for elec­
trons and holes and trap more superficially and efficiently, notably The antibacterial activity of all nanocrystals was carried out against
improve the photocatalytic activity. Staphylococcus aureus and Proteus Vulgaris bacteria (Figs. S4 and S5). The
measured ZOI is given in Table 3 and Fig. 12. All grown products showed
3.6. Mechanism better activity towards S. aureus and P. Vulgaris bacteria, but the ZLaSm
has the highest activity as compared to others. The massive production
When ZnO nanocrystals are exposed under sunlight, electron-hole of ROS species causes the demolition of mitochondria, cellular proteins,
(e-/h+) pairs created due to the movement of electrons (e-) from VB to and destruction of DNA [56]. Also, the positively charged heavy metals
the CB band. The formation of new energy or sub-bandgap states below ions Zn2+, La3+, Yb3+, Nd3+, and Sm3+ mutually interrelate with the
and above the CB by the co-doping of RE metal ions (Yb3+, Nd3+, and negatively charged cell membrane, causes the microbes death by
Sm3+) and partially filled f-orbital of RE ions can proficiently trap the e- reducing the proteins permeability. Hence the grown samples can be
that affects the charge transfer kinetics, hindering the electron-hole utilized for the treatment of these diseases. The study proposed that RE
recombination and increase charge separation efficiency [53]. The ions doped ZnO nanocrystals are feasible for biomedical applications.
trapped electron (e-) sequentially drifted to adsorb oxygen (O2), stimu­
lating the superoxide anion radicals or hydrogen peroxide and finally to 4. Conclusion
active hydroxyl radicals. On the other hand, the hole (h+) at the valence
The Zn0⋅95La0⋅05O and Zn0⋅9La0.05M0.05O (M = Yb, Nd, Sm) nano­
Table 2 crystals were prepared by the co-precipitation technique. The XRD re­
Decolourization efficiency (%), kinetic rate constant (k), and R2 values of grown sults showed that RE ions were effectively doped into the unit cell of ZnO
nanocrystals. with no secondary phase, and both single and double doping modified
their properties. The structural study showed that the prepared samples
Samples Dye Decolourization efficiency Rate constant (k) R2
(%) have tensile strain. The optical analysis results described the redshift in
energy bandgap and improvement in the optical properties of ZnO. The
ZLa MB 94 0.0766 0.8389
ZLaYb – 99 0.1278 0.9204
photocatalytic test has shown the enhancement in degradation effi­
ZLaNd – 98 0.1065 0.9556 ciency by co-doping and higher for MB dye than others under the same
ZLaSm – 99 0.1189 0.9844 conditions. The co-doped samples have excellent antibacterial perfor­
ZLa RhB 66 0.0266 0.9858 mance towards Staphylococcus aureus and Proteus Vulgaris bacteria, but
ZLaYb 83 0.0443 0.9837
La/Sm doped has the highest activity against Proteus Vulgaris. Hence,
–
ZLaNd – 78 0.0426 0.8862
ZLaSm – 89 0.0558 0.9438 this study provides the idea to alter the energy bandgap of ZnO to make
ZLa Phenol 73 0.033 0.9906 it beneficial for potential applications in optical, environmental, and
ZLaYb – 81 0.0419 0.9711 biomedical fields.
ZLaNd – 89 0.0622 0.9636
ZLaSm – 93 0.0656 0.9435

8
T. Munawar et al. Materials Science in Semiconductor Processing 122 (2021) 105485

Fig. 10. Degradation efficiency (%) (a) MB, (b) RhB, (c) Ph, in the presence of grown samples, and (d) Degradation efficiency (%) of MB, RhB, and phenol without
catalyst at different time intervals.

Fig. 11. The scheme represents the photocatalytic mechanism of grown nanocrystals for the degradation of MB and RhB dyes.

Author statement
Table 3
Antimicrobial activity of grown nanocrystals at concentrations (10%, 20%, 30%
We confirm that the manuscript has been read and approved by all
of 15 mg/mL).
named authors and that there are no other persons who satisfied the
Zone of inhibition (mm) S. aureus Zone of inhibition (mm) P. Vulgaris criteria for authorship but are not listed. We further confirm that the
Samples
10% 20% 30% 10% 20% 30% order of authors listed in the manuscript has been approved by all of us.
ZLa 9 10 10 8 10 10 We understand that the Corresponding Author is the sole contact for the
ZLaYb 8 11 13 11 12 12 Editorial process and is responsible for communicating with the other
ZLaNd 8 10 12 10 11 11 authors about progress, submissions of revisions, and final approval of
ZLaSm 9 12 13 13 16 17 proofs.

9
T. Munawar et al.
Fig. 12. Variation of the zone of inhibition (ZOI) for (a) Gram-positive Staphylococcus aureus bacteria, and (b) Gram-negative Proteus Vulgaris bacteria.
Declaration of competing interest
The authors declare that they have no known competing financial
interests or personal relationships that could have appeared to influence
the work reported in this paper.
Appendix A. Supplementary data
Supplementary data to this article can be found online at https://doi.
org/10.1016/j.mssp.2020.105485.
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