Chemosensors 09 00005 v2
Chemosensors 09 00005 v2
Chemosensors 09 00005 v2
Article
Fabrication of Zinc Oxide Nanoparticles Deposited on
(3-Aminopropyl) Triethoxysilane-Treated Silicon Substrates by
an Optimized Voltage-Controlled Electrophoretic Deposition
and Their Application as Fluorescence-Based Sensors
Fawwaz Hazzazi 1 , Alex Young 1 , Christopher O’Loughlin 1 and Theda Daniels-Race 1,2, *
1 Division of Electrical and Computer Engineering, Louisiana State University, Baton Rouge, LA 70803, USA;
fhazza1@lsu.edu (F.H.); ayoun55@lsu.edu (A.Y.); coloughlin@lsu.edu (C.O.)
2 Center for Computation & Technology, Louisiana State University, Baton Rouge, LA 70803, USA
* Correspondence: tdrace@lsu.edu
Abstract: In this study, a voltage controlled, reproducible, scalable, and cost-effective approach for
depositing zinc oxide (ZnO) nanoparticles (NPs), using electrophoretic deposition (EPD) onto p-type
silicon (Si) substrates, has been researched and analyzed for its feasibility with respect to electronic
device fabrication and fluorescence-based sensors. Our work presents a detailed investigation to
evaluate the influence of ZnO morphology, ZnO concentration, and the method of surface treatment
applied to the underlying Si substrates, because these pertain to an optimized EPD system. It has
been noted that the ZnO NP structures formed directly atop the (3-aminopropyl) triethoxysilane
(APTES)-treated Si substrates were more adhesive, thus resulting in a higher yield of NPs over that
Citation: Hazzazi, F.; Young, A.; of comparable depositions on bare silicon. Our observation is that smaller particle sizes of ZnO will
O’Loughlin, C.; Daniels-Race, T. increase the energy emission for fluorescence transmission, eliminate several peak emissions, obtain
Fabrication of Zinc Oxide higher fluorescence quantum yield (FQY) efficiency, and require less excitation energy. The results
Nanoparticles Deposited on
obtained are promising in relation to the integration of EPD in the fabrication of nano biosensors,
(3-Aminopropyl) Triethoxysilane-
PV solar cells, nano electronic devices, and thin film transistors (TFTs), where ZnO improves the
Treated Silicon Substrates by an
reliability, affordability, and increased sensitivity needed for the next generation of nanoscale devices
Optimized Voltage-Controlled
and systems.
Electrophoretic Deposition and Their
Application as Fluorescence-Based
Sensors. Chemosensors 2021, 9, 5.
Keywords: ZnO nanoparticles; voltage-controlled deposition; electrophoretic deposition; surface
https://doi.org/10.3390/ functionalization; AFM; photoluminescence
chemosensors9010005
(TFT) applications. Thus, physical properties of ZnO nanostructures are exploited in var-
ious applications including optoelectronics [20], filed emitters [21], UV lasers [22], solar
cells [23], sensors [24–29], biosensors [12,30–32], and thin film transistor (TFT) [33–36].
Deposition of ZnO nanoparticles has already been performed by physical and chemi-
cal techniques. For instance, radio frequency magnetron sputtering systems [37], pulsed
laser deposition [38], plasma enriched chemical vapor deposition (PE-CVD) [39], metal-
organic chemical vapor deposition (MOCVD) [40], sol–gel system [41], molecular beam
epitaxy [42], and atomic layer deposition [43] have been researched for their compatibil-
ity with nanomaterials and film quality for device and sensor applications. Lately, the
electrophoretic deposition method has gained increasing attention both in academia and
industrial sectors because of the wide versatility of its applications with different materials
and because of its cost-effectiveness requiring simple apparatus [44]. Additionally, the con-
trollability of the surface quality accomplished by varying the deposition parameters of the
electrophoretic deposition (EPD) system to optimize morphology, surface structures, and
optical performance [22,23]. In our previous studies, we have shown successful and con-
trollable deposition of thin carbon nanotubes films using electrospray and electrophoretic
deposition systems at room temperature (RT) without postdeposition or predisposition
annealing [45,46].
In this paper, we show the study on ZnO nanoparticles (NPs) deposited by an elec-
trophoretic deposition system at room temperature without post or pre-deposition anneal-
ing at high temperatures. The suitability of the two different surface functionalization and
the ZnO deposition yield was studied. Furthermore, the influence of the concentration
levels of ZnO in the EPD host solutions were divided into 5 and 10 wt% and its dependance
of the structural and optical features were researched. The novelty in our approach is
that we functionalized the experimental substrates by pre-deposition surface treatment,
which was (3-aminopropyl) triethoxysilane (APTES); then, we optimized the EPD colloidal
suspension for minimum surface defects and better electrophoretic deposited ZnO NP
structures on p-silicon substrates. We believe that this, and other steps taken in this study,
differentiates our work from that of other groups using EPD. The application of the studied
surface as smoothness, crystallinity, and transparent conductive electrodes was exhibited
and examined.
Chemosensors 2021, 9, 5 silicon wafers (boron dopant; resistivity = 10−20 ohm-cm; <100> orientation) from3Shin- of 13
Etsu Handotai (SEH) (Tokyo, Japan). The electrodes for the EPD setup consisted of a 2 × 1
cm2 platinum (Pt) anode and a 2 × 1 cm2 p-type silicon cathode. Ethanol (C2H5OH) was
usedused
was for preparation of the
for preparation of EPD ZnOZnO
the EPD NP solution. For cleaning
NP solution. purposes,
For cleaning we used
purposes, nitric
we used
acid (HNO 3), hydrochloric acid (HCl), and acetone, which were obtained from Fisher Sci-
nitric acid (HNO3 ), hydrochloric acid (HCl), and acetone, which were obtained from Fisher
entific Lab
Scientific Supplies
Lab (Fair
Supplies Lawn,
(Fair NJ,NJ,
Lawn, USA).
USA).
2.2. EPD
2.2. EPD Deposition
Deposition Setup
Setup
Undoped 11wt%,
Undoped wt%,55wt%,
wt%,andand1010wt%
wt%ZnOZnOnanoparticle
nanoparticlesolutions
solutionswere
weredeposited
depositedby by
theelectrophoretic
the electrophoretic method
method using
using the
the vertical
vertical set-up
set-up presented
presented ininFigure
Figure1.1. The
The frame
frame (6)
(6)
was aa 3D-printed
was 3D-printed glass-filled polyamide
polyamide with dimensionsofof5050× ×
withdimensions 5050 × cm
× 50 and
50 3cm 3 and
the sub-
the
substrate
strate (3)(3)
was was a platinum
a platinum (Pt)
(Pt) plateheated
plate heatedatat200 ◦ Cby
200°C bythe
thethermo-controlled
thermo-controlled heater (6). (6).
The
Theplatinum
platinumtotosilicon
siliconsamples
samplesdistance
distancewas
was2 2cmcmand
anda voltage
a voltageofof
3030VVwas
wasapplied
appliedviavia
a
DC power supply (Applied Kilovolts, Sussex, UK). The EPD solvent was
a DC power supply (Applied Kilovolts, Sussex, UK). The EPD solvent was placed in a 20 placed in a 20
mL
mL beaker
beaker (2)(2)positioned
positioned in
in the
themiddle
middle ofofthe
theEPD
EPDsetup
setup(Figure
(Figure1).
1). The
The Pt
Ptelectrode
electrode (3)
(3)
and
andSiSisubstrates
substrates(4)(4)were
wereplaced
placedinto
intothe
theEPD
EPDsolution
solution(2)
(2)and
andconnected
connectedto toaaDC
DCvoltage
voltage
source
source(1).
(1).
Figure1.1.Schematic
Figure Schematicdiagram
diagramofofthe
theEPD
EPDsystem
systemset-up:
set-up:1—DC
1—DCvoltage
voltage source;
source; 2—EPD
2—EPD ZnO
ZnO solu-
solution;
tion; 3—Platinum (2 × 1
2 cm 2 electrode); 4-silicon substrate; 5—connectors; 6—EPD base; 7—adjust-
3—Platinum (2 × 1 cm electrode); 4-silicon substrate; 5—connectors; 6—EPD base; 7—adjustable
able contact length of electrodes within the electrolyte; 8—adjustable distance between electrode
contact length of electrodes within the electrolyte; 8—adjustable distance between electrode and sub-
and substrate.
strate.
2.3. Electrodes
2.3. ElectrodesPreparation
Preparation
Prior to the deposition
Prior depositionof ofZnO
ZnONP NPonto thethe
onto electrodes
electrodes viavia
EPD,EPD,we we
cleaned the sub-
cleaned the
strates thoroughly
substrates thoroughly by sonication
by sonication in an in acetone
an acetone bathbath
for 2for
h followed
2 h followedby cleaning withwith
by cleaning HCl
and and
HCl isopropyl alcohol
isopropyl (IPA)(IPA)
alcohol sequentially.
sequentially.Next,Next,
substrates werewere
substrates treated in a heated
treated pira-
in a heated
nha suspension (H SO :H O ) for 1 h to ensure removal of any
piranha suspension (H2 SO4 :H2 O2 ) for 1 h to ensure removal of any organic material,
2 4 2 2 organic material, followed
by soaking
followed byand a wash
soaking and inadeionized (DI) water(DI)
wash in deionized for 1water
min. Finally,
for 1 min.theFinally,
substrates were dried
the substrates
by nitrogen
were dried bygas. It is worth
nitrogen gas. Itmentioning that the previous
is worth mentioning procedure
that the previous of substrate
procedure cleaning
of substrate
was conducted
cleaning only for silicon
was conducted only for samples. However,However,
silicon samples. for electrodes, platinum platinum
for electrodes, (Pt) and steel,
(Pt)
we soaked
and steel, wethese
soakeditemstheseforitems
10 min for in
10 warm
min in HNO
warm3 HNO to remove
3 to impurities,
remove followed
impurities, by
followed 10
by
min10 in
min in warm
warm KOH KOH andand a soak
a soak in in
DIDI water
water forfor2020min
min(Figure
(Figure 2c).
2c). The electrophoretic
electrophoretic
deposition
deposition of of ZnO
ZnO NPs NPs waswas carried
carried outout ininaatwo-electrode
two-electrodedeposition
depositionsetup,
setup,where
wherethe the
metal
metalelectrode
electrodeserve
serveas asthe
theanode
anodeand andthethetarget
targetsubstrates
substratesserveserveas asthe
thecathode.
cathode.
Chemosensors 2021, 9, 5 4 of 13
Chemosensors 2021, 9, x FOR PEER REVIEW 4 of 13
(a) (b)
(c) (d)
Figure 2.
Figure 2. (a)
(a)Cleaned
Cleanedsilicon
siliconsample
sampleandandplatinum sample
platinum (electrode).
sample (b) (b)
(electrode). ZnO nanopowder
ZnO as- as-
nanopowder
purchased from Sigma-Aldrich (catalog number 677450). (c) Substrate treated by warm piranha
purchased from Sigma-Aldrich (catalog number 677450). (c) Substrate treated by warm piranha
solution and (d) Silicon substrate treated by APTES solution prepared for ZnO electrophoretic
solution and (d) Silicon substrate treated by APTES solution prepared for ZnO electrophoretic
deposition.
deposition.
2.4. 3-Aminopropyl-Triethoxysilane
2.4. 3-Aminopropyl-Triethoxysilane (APTES) (APTES) Surface
Surface Functionalization
Functionalization Treatment
Treatmentofof ZnO
Substrates
ZnO Substrates
has been
It has beenshown
shownininthe theliterature
literature that
that 3-aminopropyl-triethoxysilane
3-aminopropyl-triethoxysilane (APTES)
(APTES) sur-
surface
face functionalization
functionalization can becanused
be used to increase
to increase surface
surface adhesion,
adhesion, improve
improve filmfilm quality,
quality, and and
im-
immobilize
mobilize material
material on substrates
on substrates for biomaterial
for biomaterial sensorssensors [25,26].
[25,26]. In ourInwork,
our work, we im-
we immersed
mersedsilicon
p-type p-typesamples
silicon samples
in a heated in asolution
heated solution
of APTES of and
APTES and ethanol
ethanol (volume(volume
ratio 1:5)ratio
for
45
1:5)min. Thereafter,
for 45 we driedwe
min. Thereafter, these samples
dried these in a standard
samples electronics
in a standard laboratory
electronics oven for
laboratory
50
ovenmin.forFigure
50 min.2c shows
Figure the Si substrate
2c shows the Sisurfaces
substrateafter APTESafter
surfaces treatment.
APTESFrom Figure From
treatment. 2d, it
is clear 2d,
Figure thatita is
new layer
clear of aAPTES
that is on of
new layer theAPTES
substrate.
is onFigure 2c, captured
the substrate. after2c,
Figure thecaptured
piranha
cleaning, introduced
after the piranha a soft and
cleaning, clean layer
introduced of hydroxyl
a soft and cleangroups
layer ofonto the p-type
hydroxyl Si substrates
groups onto the
by hydroxylation
p-type Si substrates procedure. Afterwards,
by hydroxylation we continued
procedure. the salinization
Afterwards, we continued procedure with
the saliniza-
the hydrolysis of ethoxy (–C2H5) groups from the APTES molecules,
tion procedure with the hydrolysis of ethoxy (–C2H5) groups from the APTES molecules, continuing to the
creation of a silanol rough layer (Si–O–H) which enhanced the adhesion
continuing to the creation of a silanol rough layer (Si–O–H) which enhanced the adhesion of nanomaterials
structures [47]. structures [47].
of nanomaterials
3. Results
We started our study by optimizing the EPD chemical solutions of ZnO precursor in
order to obtain smooth, flat microstructures and surfaces with good electrical characteristics
and minimum elastic deformation. Three different concentrations of ZnO were used in
this investigation: 1, 5 and 10 wt% of ZnO nanoparticles, where the solvent consisted of
ethanol and DI water (see Table 1). A 50 nm and 100 nm BET (Brunauer–Emmett–Teller)
instrument was used to study the influence of the nanoparticles’ diameters on the surface
morphology and nanoelectronics device performance.
3.1. Fluorescence Spectra for Sensing ZnO Microparticles and Nanoparticles in DI Water
We investigated the impact of particle size on the photoluminescence of ZnO mixed
with DI water and the sensitivity of ZnO nanoparticles. We analyzed the fluorolog emission
and excitation spectra of the EPD suspension. Figure 1 shows normalized fluorescence
emission and excitation spectra of ZnO microparticles mixed with DI water by using a
Fluorolog® -3 spectrofluorometer system for a fixed excitation wavelength (λf = 315 nm).
The strong intensity emission peak wavelength and the full width at half-maxima (FWHM)
are 383 nm (energy equivalent to E peak-ems-micro = 3.2 eV blue range) and 32 nm,
respectively. Additionally, there were other weak UV deep-level emissions whose peak
wavelength were 355 nm (3.4925 eV) and 337 nm (3.679 eV). On the excitation spectrum, the
highest intensity excitation peak wavelength recorded and the full width at half-maxima
(FWHM) were 312 nm (energy equivalent to EPeak-ext = 3.9739 eV) and 43 nm, respectively.
We obtained the integral over the whole emission spectrum to evaluate the fluorescent
quantum yield (FQY) of ZnO NPs immersed in H2 O (pure water) which was 0.35. We used
the following relationship [48]:
Z ∞
ΦF = Fλ f (λ)dλ (1)
0
where ΦF is the fluorescence quantum yield of ZnO and Fλf (λ) is the emission spectrum of
ZnO obtained from the Fluorolog® -3 spectrofluorometer system.
Researchers use ΦF to calculate the efficiency of the fluorescence process. There
are other methods (relative [49–56] and absolute [51,57–59] measurement of quantum
yields and the MATLAB [60] toolbox) proposed by several researchers. We used the
absolute measurement with standardized procedure mentioned in sample preparation
and wavelength [55]. It is worth mentioning that the fluorescence spectrum (emission
spectrum) in Figure 5A reflects the ZnO microparticle distribution of the probability of the
various transitions from the lowest energy an electron can occupy when it gains energy
(photon or phonon) S1 to various energy levels in the ground state (original position of an
electron) S0. It illustrates that the probability of an electron transitioning on a wavelength
at 383 nm which corresponds to (ENP = 3.24 eV) is the highest on the wavelength spectrum.
The calculated energy loss of electrons transitioning from the excited state (excitation
spectrum) to the ground state (emission spectrum) is 0.7367 eV by using Strokes shift
(wavelength) [61].
∆λ = λ f − λ a (2)
Chemosensors 2021, 9, x FOR PEER REVIEW 7 of 13
to the ground state (emission spectrum) is 0.7367 eV by using Strokes shift (wavelength)
Chemosensors 2021, 9, 5 [61]. 7 of 13
Δλ=λ f − λa (2)
is the
where λff is the maximum
maximum wavelength
wavelength of the fluorescence
fluorescence emission,
emission, and
and λλaa is the maximum
wavelength of the absorbed spectrum.
Figure 5.
Figure 5. (A)
(A)microparticles
microparticlesemission
emissionand
andexcitation
excitationspectrum
spectrumofof
ZnO,
ZnO,(B)(B)
ZnO ZnONPs emission
NPs andand
emission excitation spectrum,
excitation (C)
spectrum,
ZnOZnO
(C) particle sizesize
particle fluorescent emission
fluorescent contrast,
emission andand
contrast, (D)(D)
ZnO particle
ZnO sizesize
particle fluorescent excitation
fluorescent contrast.
excitation contrast.
We repeated
repeatedthe theaforementioned
aforementioned processes
processes withwith
ZnOZnO nanoparticle
nanoparticle samples samples
immersedim-
mersed
in DI waterin DI(30 water
mL) (30
undermL)similar
under conditions
similar conditions
to presentto apresent a comparison
comparison analysis analysis
of particleof
particle size on
size effects effects
the onZnOthefluorescence
ZnO fluorescence spectrum.
spectrum. Figure Figure 5B shows
5B shows oneone strong
strong inten-
intensity
sity emission
emission peakpeak wavelength,
wavelength, the full
the full widthwidth at half-maxima
at half-maxima (FWHM),
(FWHM), fluorescent
fluorescent quan-
quantum
tum
yield,yield, and Stroke
and Stroke shift shift
energy energy
are 399arenm 399(energy
nm (energy equivalent
equivalent to EPeak-ems-nano
to EPeak-ems-nano = 3.1074
= 3.1074 eV
(blue
eV range)),
(blue range)),60 60
nm,nm,0.5182,
0.5182,andand0.971
0.971eV,eV,respectively.
respectively.On Onthe
theexcitation
excitation spectrum
spectrum of
NPs,the
ZnO NPs, thehighest
highestfluorescence
fluorescenceintensity
intensity excitation
excitation peakpeak wavelength
wavelength recorded
recorded andandthe
the full
full widthwidth at half-maxima
at half-maxima (FWHM)
(FWHM) werewere
304 nm304 (energy
nm (energy equivalent
equivalent to EPeak-ext-nano
to EPeak-ext-nano = 4.0784=
4.0784
eV) andeV) 27and
nm,27respectively.
nm, respectively.
Table Table
2 shows 2 shows highlighted
highlighted results
results fromfrom the emission
the emission and
and excitation
excitation spectra
spectra of different
of different ZnOZnO particle
particle sizes.sizes.
We explain the observed emission mechanisms mechanisms of of ZnO
ZnO NP NP fluorescence
fluorescence as as the
the fol-
fol-
lowing. The 399
lowing. The 399 nm (3.1 nm (3.1 eV) ultraviolent
ultraviolent range emission might relate to the inter-band
radiation sequence
radiation sequence of of photogenerated
photogenerated electronselectrons andand holes.
holes. Typically,
Typically, light
light isis emitted
emitted by by
an electron
an electron carry
carry energy
energy equal
equal toto or
or slightly
slightly higher
higher than
than thethe direct
direct bandgap
bandgap energy.
energy. Ac-
Ac-
cording to
cording to Li
Li et
et al.
al. [62],
[62], the
the fluorescence
fluorescence emissions
emissions of of ZnO
ZnO quantum
quantum dots,dots, synthesized
synthesized at at
the [LiOH]/[Zn21] ratio of 1:3 and dispersed in water, were 525 nm
the [LiOH]/[Zn21] ratio of 1:3 and dispersed in water, were 525 nm (less than ZnO energy (less than ZnO energy
bandgap emission)
emission) withwithlow lowintensity
intensity(fraction
(fractionofof1010 4 ) when it was excited by UV light
bandgap 4) when it was excited by UV light at
at 302
302 nm.nm. AA fluorescence
fluorescence emission
emission withenergy
with energyhigher
higherthan
thanthethebandgap
bandgap was was reported.
reported.
Zhang et al. [63] deposited ZnO films by using a sputtering system
Zhang et al. [63] deposited ZnO films by using a sputtering system onto an Si substrate onto an Si substrate
and reported
and reported aa 290 290 nm
nm emission
emission peak.
peak.
Chemosensors 2021, 9, 5 8 of 13
Table 2. Summary of ZnO NPs fluorescence of EPD solution samples. Fluorescence spectrometer of ZnO particles immersed
in DI water under fixed wavelength (λ = 315 nm).
Stoke
Emission Excitation
Shift
Point of Study
Peak Energy FWHM FQY Peak Energy FWHM Energy
Particles Sizes Wavelength (nm) (eV) (nm) Wavelength (nm) (eV) (nm) (eV)
ZnO nanoparticles 399 3.10 60 0.52 304 4.08 27 0.971
ZnO microparticles 383 3.24 32 0.35 312 3.98 43 0.74
emosensors 2021, 9, x FOR PEER REVIEW The hole at the edge (0.8 µm) of the surface area indicates that the increased thickness
9 of 13 with
60 V applied voltage was 4 nm thicker on average.
Figure
Figure 6. Structure 6. Structure
study study of electrophoretic
of electrophoretic deposited ZnO deposited
NPs. WeZnO NPs. We
examined examined
the the surface and
surface uniformity uni- roughness
by atomic forceformity and roughness
microscopy (AFM). 2Dby atomic
AFM forceofmicroscopy
images (AFM).
the ZnO thin films2D
EPDAFMwithimages of the
different ZnO thin
applied films(A) 10 V;
voltage:
(B) Surface profile of the blue line on (A); (C) 60 V with APTES; and (D) Surface profile of the blue line on (C). V
EPD with different applied voltage: (A) 10 V; (B) Surface profile of the blue line on (A); (C) 60
with APTES; and (D) Surface profile of the blue line on (C).
Figure 7A–F shows 3D images of EPD ZnO nanoparticles on p-type silicon samples
Figureand7A–Ftheshows 3D images
influence of EPDdifferent
of applying ZnO nanoparticles
EPD voltages. on p-type
Whensilicon samples
the applied EPD system
and the influence
voltageofincreased
applyingin different
the EPD EPD voltages.
solution fromWhen theV,applied
5 to 60 EPD system
the average volt- of the thin
thicknesses
age increased
filminonthetheEPD solution
p-type from 5were
substrate to 60also
V, the average thicknesses
increased. Figure 7A–Fofalso the thin
showsfilmthat when a
on the p-type substrate were also increased. Figure 7A–F also shows that when
higher voltage was applied on the ZnO thin film, the overall surface roughness and surface a higher
voltage wasuniformity
applied on the ZnO The
increased. thin surface
film, the overall associated
structure surface roughness
with 60 V and surface
(Figure 7C)uni-
was smoother
formity increased.
than 10 V TheEPD surface
appliedstructure
voltageassociated
(Figure 7A) with
with 60fewer
V (Figure
grains7C)on was smoother
the surface and less ZnO
than 10 V EPD applied voltageThe
NP agglomeration. (Figure
grain7A)sizewith
andfewer
thicknessgrains on the surface
increased and less
as the applied ZnO increased.
voltage
NP agglomeration. The grain
Thus, an increase sizeEPD
in the andapplied
thickness increased
voltage on the asZnO theNPsapplied
surfacevoltage
improves in- the overall
creased. Thus, an increase
crystalline in the
structure ofEPD applied
deposited ZnOvoltage
NPs on onP-type
the ZnO NPs substrates.
silicon surface improves
This is confirmed
the overall by
crystalline
the AFMstructure
analysis.ofThe deposited
improved ZnO NPs on P-type
uniformity silicon substrates.
with applied voltage may This
be due to the
is confirmed by the AFM
increase in zeta analysis.
potentialTheinimproved
the EPD uniformity
setup which with applied
leads voltagediffusivity
to a higher may be of ZnO
due to the increase
particles in in zeta potential
the EPD in the
solution EPD setup
[45,68]. which leads
The formation of a to a higher
large islanddiffusivity
structure associated
of ZnO particles in the EPD
with higher appliedsolution
voltage[45,68].
may beThedue
formation
to the EPDof aZnO
largeNPs,
island structure
which as- with the
coalesced
sociated with higher
bipolar ZnO applied voltage
thin film. Figuremay 7Dbeshows
due to thethe EPD ZnO
influence NPs, whicha coalesced
of depositing heated APTES layer
as a functionalization
with the bipolar ZnO thin film. Figure surface7D layer on bare
shows p-type silicon
the influence substratesa before
of depositing heateddepositing
a ZnO layer. We observed that APTES-treated surfaces
APTES layer as a functionalization surface layer on bare p-type silicon substrates before showed better results in terms
depositing of uniformity,
a ZnO layer. We fewer grains,that
observed andAPTES-treated
controllable ZnO thickness.
surfaces showed With increasing
better results the grain
in terms of size, the surface
uniformity, fewer ofgrains,
the thin andstructures on p-type
controllable silicon substrate
ZnO thickness. formed island-shaped
With increasing the
grain size, structures
the surfacethat of led
the to rougher
thin surfaces
structures [69,70]. silicon substrate formed island-
on p-type
shaped structures that led to rougher surfaces [69,70].
Chemosensors 2021,
Chemosensors 2021,9,
9,5x FOR PEER REVIEW 10 of
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13
Figure 7.
Figure 7. AFM
AFM 3D3D thickness
thickness measurements
measurements of of ZnO
ZnO structures
structures with
with different
different applied
applied voltage
voltage EPD
EPD system.
system. ZnO
ZnO surfaces
surfaces
deposited with
deposited with different
different voltages:
voltages: (A) 10 V;
(A) 10 V; (B)
(B) 30
30 V;
V; (C)
(C) 60
60 V;
V;(D)
(D)APTES
APTES functionalized
functionalized substrate
substrate with
with 10
10 V;
V; (E)
(E) APTES
APTES
functionalized substrate with 60 V; and (F) thickness profile of (E).
functionalized substrate with 60 V; and (F) thickness profile of (E).
4. Discussion
4. Discussion
In this communication, our present investigation has demonstrated that morphology
In
controlledthisZnO
communication,
nanoparticles our(NPs)
presentcaninvestigation
be successfully has deposited
demonstrated via athat morphology
system of elec-
controlled ZnO nanoparticles (NPs) can be successfully deposited
tronic deposition with synthesized organic solvent as the EPD solution and be via a system of electronic
exploited
deposition with synthesized
as fluorescence-based sensors organic solvent as
for the detection of the
ZnOEPD solution
particle sizes.and
Thisbestudy
exploited as
was car-
fluorescence-based sensors for the detection of ZnO particle sizes.
ried out through synthesizing EPD solvent, microfabricating samples, functionalizing This study was carried
out through synthesizing
substrates, characterizing EPD solvent,
with microfabricating
fluorologs and AFM, samples, functionalizing
and sensing particlesubstrates,
sizes via
characterizing with fluorologs and AFM, and sensing particle
fluorolog spectra. The fluorolog photoluminescence properties of the ZnO NPs and sizes via fluorolog spectra.
mi-
The fluorolog photoluminescence properties of the ZnO NPs and
croparticles mixed with DI water highly influence the energy emission for fluorescence microparticles mixed
with DI water highly
transmission, eliminateinfluence
severalthe energy
peak emission
emissions, for fluorescence
obtain higher FQYtransmission,
efficiency, and eliminate
require
several peak emissions, obtain higher FQY efficiency, and require
less excitation energy. Hence, compared with other EPD solutions, ZnO NP surfaces less excitation energy.
syn-
Hence,
thesized by using a minimum surface tension solvent such as ethylene glycol obtain aa
compared with other EPD solutions, ZnO NP surfaces synthesized by using
minimum
better-qualitysurface tension
grain size, solvent
higher such as ethylene
transmittance ofglycol obtain emission
fluorescent a better-quality grain with
associated size,
higher transmittance of fluorescent emission associated with small particle sizes, and better
small particle sizes, and better crystallite quality. It was observed that there was a strong
crystallite quality. It was observed that there was a strong influence of the applied voltage,
influence of the applied voltage, ZnO concentration, and APTES-treated substrates on the
ZnO concentration, and APTES-treated substrates on the overall morphology, coverage,
overall morphology, coverage, thickness, and flatness of deposited nanostructures. We
thickness, and flatness of deposited nanostructures. We observed that APTES-treated
observed that APTES-treated surfaces showed better results in terms of uniformity, fewer
surfaces showed better results in terms of uniformity, fewer grains, and controllable ZnO
grains, and controllable ZnO thickness. We showed that increasing the EPD applied volt-
thickness. We showed that increasing the EPD applied voltage can improve the coverage,
age can improve the coverage, adhesion, and the uniformity of ZnO NP nanostructures.
adhesion, and the uniformity of ZnO NP nanostructures. Our work in this direction will
Our work in this direction will focus on reproducibility tests, depositing ZnO NPs onto p-
focus on reproducibility tests, depositing ZnO NPs onto p-type doped direct bandgap
type doped direct bandgap semiconductors, such as GaAs, as well as sapphire substrates
semiconductors, such as GaAs, as well as sapphire substrates to test the performance of
to test the performance of ZnO/substrate heterojunctions. We will take current–voltage
ZnO/substrate heterojunctions. We will take current–voltage characteristics of our current
characteristics of our current samples. Other experimental possibilities include introduc-
samples. Other experimental possibilities include introducing channels in our substrates
ingusing
by channels in our substrates
lithography to ensure theby accumulation
using lithography of ZnO to nanoparticles
ensure the accumulation
in designated ofareas
ZnO
nanoparticles in designated areas and examining our samples by
and examining our samples by atomic force microscopy (AFM) to study sample topology. atomic force microscopy
(AFM)
We willto study
also sample topology.
experiment We will variation
with introducing also experiment withsystem
to the EPD introducing variationthe
via changing to
the EPD system
distance between via changing length
electrodes, the distance between
of contact withelectrodes,
electrolytes,length of contact
electrode with elec-
materials, and
trolytes, electrode materials, and electrolyte composition. A device
electrolyte composition. A device performance study based on the EPD of ZnO on p-silicon performance study
based
is also on the EPD of ZnO on p-silicon is also in progress.
in progress.
Chemosensors 2021, 9, 5 11 of 13
5. Conclusions
APTES functionalized silicon surfaces perform better with EPD of ZnO NPs than
non-functionalized substrates in terms of adhesion, uniformity, and surface roughness. We
used the fluorolog properties for distinguishing and sensing the ZnO particle sizes. The
energy emission was highly influenced by the ZnO particle size. The results obtained can
enhance the integration of EPD of ZnO NPs in the microfabrication of sensors, materials
for nano electronics devices, and thin film transistors (TFTs), where ZnO NPs improve
the reliability, affordability, and increased sensitivity needed for the next generation of
nanoscale devices and systems.
Author Contributions: Conceptualization, T.D.-R.; data curation, F.H.; formal analysis, F.H.; funding
acquisition, T.D.-R.; investigation, T.D.-R.; methodology, T.D.-R.; project administration, T.D.-R.;
resources, A.Y., C.O. and T.D.-R.; software, T.D.-R.; supervision, T.D.-R.; validation, T.D.-R.; writing—
original draft, F.H.; writing—review and editing, T.D.-R. All authors have read and agreed to the
published version of the manuscript.
Funding: This work was partially funded by the Louisiana Board of Regents LIFT2 grant (LSU-
2018-LIFT 002) and the LSU Foundation project #104454-340 as created through the generosity of Dr.
Kristina M. Johnson.
Institutional Review Board Statement: Not applicable.
Informed Consent Statement: Not applicable.
Data Availability Statement: Data sharing not applicable.
Acknowledgments: The authors also wish to recognize the staff and appreciate the use of the
Electronic Materials & Devices Laboratory (EMDL) housed in the Division of Electrical & Computer
Engineering at Louisiana State University.
Conflicts of Interest: The authors declare no conflict of interest.
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