coatings

Review
Thin-Film Coating Methods: A Successful Marriage of
High-Quality and Cost-Effectiveness—A Brief Exploration
Muhammad A. Butt

Institute of Microelectronics and Optoelectronics, Warsaw University of Technology,

Koszykowa 75, 00-662 Warszawa, Poland; [email protected]

Abstract: In this review, several cost-effective thin-film coating methods, which include dip-coating,
spin-coating, spray-coating, blade-coating, and roll-coating, are presented. Each method has its
own set of advantages and disadvantages depending on the proposed application. Not all of them
are appropriate for large-scale production due to their certain limitations. That is why the coating
method should be selected based on the type and size of the substrate, including the thickness and
surface roughness of the required thin films. The sol–gel method offers several benefits, such as
simplicity in fabrication, excellent film uniformity, the capacity to cover surfaces of any size and over
vast areas, and a low processing temperature. Nevertheless, these coating methods are somewhat
economical and well managed in low-budget laboratories. Moreover, these methods offer thin films
with good homogeneity and low-surface roughness. Furthermore, some other thin-film deposition
methods, for instance, physical vapor deposition (PVD) and chemical vapor deposition (CVD), are
also discussed. Since CVD is not restricted to line-of-sight deposition, a characteristic shared by
sputtering, evaporation, and other PVD methods, many manufacturing methods favor it. However,
these techniques require sophisticated equipment and cleanroom facilities. We aim to provide the
pros and cons of thin-film coating methods and let the readers decide the suitable coating technique
Citation: Butt, M.A. Thin-Film
for their specific application.
Coating Methods: A Successful
Marriage of High-Quality and
Cost-Effectiveness—A Brief
Keywords: dip-coating; spin-coating; roll-coating; blade-coating; spray-coating; physical vapor deposition;
Exploration. Coatings 2022, 12, 1115. chemical vapor deposition; flame hydrolysis deposition; sputtering
https://doi.org/10.3390/
coatings12081115

Academic Editors:
1. Introduction
Alexander G. Ulyashin
and Aomar Hadjadj Coating is the way of incorporating a thin coating of material into a substrate by depo-
sition in either the liquid phase (solution) or the solid phase (powder or nanoparticles) [1].
Received: 6 July 2022
The use of coating strategies may be tailored to meet production requirements for coated
Accepted: 3 August 2022
layer thickness, coated surface roughness, rate, and coating product size, which can be
Published: 4 August 2022
defined by coating velocity, coated film width, and patterning capabilities [2]. The coating
Publisher’s Note: MDPI stays neutral operation may be carried out at air pressure or low vacuum conditions. It is categorized
with regard to jurisdictional claims in according to the solubility of the coating components used. In solution coating, a binder
published maps and institutional affil- and target material are dissolved in a solution that may coat the substrate directly, and the
iations. solution then evaporates from the resultant wet film to produce a dry film. As opposed
to this, vacuum deposition techniques including chemical vapor deposition (CVD) [3],
physical vapor deposition (PVD) [4], atomic layer deposition (ALD) [5], plasma [6], flame
hydrolysis deposition (FHD) [7,8], and sputtering [9] are mostly used to produce thin,
Copyright: © 2022 by the author.
conductive [10], semi-conductive [11] and dielectric layers of demanded morphology that
Licensee MDPI, Basel, Switzerland.
are utilized to transfer heat or electricity under low- or high-vacuum conditions. The
This article is an open access article
guiding layer must have a higher refractive index than the substrate and cladding to ef-
distributed under the terms and
fectively confine light [12,13]. Consequently, thin-film deposition and local bulk material
conditions of the Creative Commons
Attribution (CC BY) license (https://
manipulation are the two major methods that may be used to execute the guiding layer. The
creativecommons.org/licenses/by/
thin-layer deposition method includes procedures such as radio frequency (RF)-sputtering
4.0/).
and magnetron sputtering, CVD, plasma-enhanced CVD, FHD, spray pyrolysis deposition,

Coatings 2022, 12, 1115. https://doi.org/10.3390/coatings12081115 https://www.mdpi.com/journal/coatings

Coatings 2022, 12, 1115 2 of 22

pulsed laser deposition, spin-coating, spray-coating, and sol–gel coating. The direct inscrip-
tion of a channel waveguide (WG) in the substrate using an femtosecond (FS)-laser is an
alternative to performing local modifications of the bulk material via ion exchange, ion
implantation, or UV radiation.
Using the roll-coating process, a surface is coated with a tiny, micro nanoscale layer of
liquid that has been recirculated across a sheet or web. The major goals of the thin layer
coating are to increase the surface’s effectiveness, service life, and quality. The coating is
widely employed at the industrial level due to its useful benefits and applicability. The
manufacturing of paper, paperboard, cellulose thin films, plastic coatings, fibrous fabric
sheets, metallic foils, etc. are only a few of the processes in which it is primarily utilized.
Most of the chemicals employed in the roll-coating procedure are non-Newtonian fluids
that behave in either a viscoelastic or pseudoelastic manner [14,15].
Due to its effective material utilization and direct and accurate patterning with a
resolution of 20–30 mm, in contrast to spin-coating as well as other traditional processes,
ink-jet printing techniques have drawn interest as a potentially cost-effective way for
fabricating Perovskite solar cells (PSCs) [16–18]. Regrettably, because of its complexity and
poor volume output, ink-jet printing cannot be easily adapted to mass production [19].
With no restrictions on substrate size and minimal polymer use, spray-coating techniques
offer a promising future for large-scale manufacturing [20]. They are expected to replace
spin-coating methods, the industry standard. The capacity to access a wide range of fluids
with different rheology makes it possible to produce completely spray-coated PSC devices.
Yet, the use of spray coating in the manufacture of PSC is constrained by the following
major problem: a thicker and more uneven layer [21]. Therefore, most current research
focuses on improving the morphology of an active layer employing high boiling point
solvents [22], additives, solvent combinations, post-thermal annealing, and other spray
coating techniques [22].
Spin-coating is a rapid and popular method for depositing thin films on substrates,
and its main benefit is that it is simple to create extremely uniform films. When a solution
of a particular substance is spun at a fast speed, the centripetal force and the liquid’s surface
tension work together to cover the substrate uniformly. Spin-coating produces a thin film
with a thickness of a few nm(s) to a few microns after the surplus solvent is removed. Small
substrates that range in size from a few millimeters square to a meter or more in diameter
are coated using the spin-coating process. The convenience and relative ease of setting
up the process, together with the thinness and homogeneity, are the main benefits of the
spin-coating approach.
The dip-coating technique is a quick, easy, affordable, and high-quality coating method
that is utilized in both industrial and lab applications [23]. The dip-coating method is fre-
quently used for optical coatings, including large-area antireflective coatings for sun control
glasses and the manufacture of vehicle rear mirrors. In the dip-coating procedure, a sub-
strate is submerged in a solution of coating components before the solution is drained away.
The procedure may be described as the solution-based deposition of an aqueous-based
liquid phase onto a substrate’s surface. The requisite material is typically dissolved in solu-
tions and directly applied to the substrate surface. There are several complicated chemical
and physical variables used in the dip-coating process. The duration of immersion, speed
of withdrawal, dip-coating cycles, density and viscosity, surface tension, substrate surface,
and coating solution evaporation factors all affect the thickness and shape of the film.
The paper is arranged as follows: Section 2 presents the basic mechanism and the recent
advancements in the dip-coating method. It is one of the easiest and most common methods
for producing thin films from a wide range of inorganic, hybrid, and nanocomposite
materials. In the spin-coating method, a tiny drop of coating material is put into the
substrate’s center before the substrate is rotated at a regulated high speed. The size of
the substrate is one of the key drawbacks of spin-coating. High-speed spinning is more
challenging as the size goes up since film thinning gets more challenging. The working
mechanism and recent progress in this technology are presented in Section 3. Roll-coating is
Coatings 2022, 12, x FOR PEER REVIEW 3 of 23

challenging as the size goes up since film thinning gets more challenging. The working
Coatings 2022, 12, 1115 mechanism and recent progress in this technology are presented in Section 3. Roll-coating 3 of 22
is a pre-metered coating that applies coating liquid to a substrate using a succession of
rollers. The amount of coating material provided to the substrate is practically independ-
aent of the characteristics
pre-metered and structures
coating that applies of theto
coating liquid fabric because
a substrate a metered
using layerofofrollers.
a succession the coating
liquid
The is first
amount generated
of coating on the
material roller to
provided surface before isit practically
the substrate is transferred to the substrate
independent of the as
discussed in Section
characteristics 4. Section
and structures 5 presents
of the the traditional
fabric because a meteredspray-coating method
layer of the coating thatisis still
liquid
first
the generated
most often onreported
the roller due
surface before
to its lowitcost
is transferred
and lack to of the substrate equipment,
specialized as discussed though.
in
Section 4. Section 5 presents the traditional spray-coating method that
Some equipment is connected to compressors for photocatalytic coating so that the solu- is still the most often
reported
tion existsdueat to the
its low cost and
desired lackand
speed of specialized
pressure.equipment,
Similar to though. Some equipment
the dip-coating technique,is the
connected
solution mustto compressors for photocatalytic
be correctly prepared before coating
being so loaded
that the into
solution
the exists
spray.atBlade
the desired
coating of-
speed and pressure. Similar to the dip-coating technique, the solution must be correctly
fers the benefits of large-area homogeneity, little material waste, interlayer dissolution
prepared before being loaded into the spray. Blade coating offers the benefits of large-area
prevention, compatibility with roll-to-roll manufacturing, and more efficient use of active
homogeneity, little material waste, interlayer dissolution prevention, compatibility with
material while still allowing for the preparation of well-defined films as discussed in Sec-
roll-to-roll manufacturing, and more efficient use of active material while still allowing for
tion
the 6. Moreover,
preparation there are several
of well-defined films as other noteworthy
discussed in Sectionphysical
6. Moreover,and there
chemical deposition
are several
methods
other available
noteworthy and being
physical and widely
chemical used in research
deposition and industry,
methods available such as physical
and being widelyvapor
used in research and industry, such as physical vapor deposition (PVD) and chemical vaporin Sec-
deposition (PVD) and chemical vapor deposition (CVD), which are also discussed
tion 7. Additionally,
deposition (CVD), which theare
paper
also ends with in
discussed a fine discussion
Section and the the
7. Additionally, author’s
paperopinion
ends on
coating
with a finemethods
discussion in and
Section 8. For quick
the author’s navigation
opinion on coatingofmethods
the paper’s content,
in Section thequick
8. For graphical
navigation
illustrationofisthe paper’s
given content,
in Figure 1. the graphical illustration is given in Figure 1.

Figure1.1.Graphical
Figure Graphicalillustration of the
illustration optical
of the thin-films
optical coating
thin-films methods
coating discussed
methods in thisin
discussed review.
this review.
2. Dip-Coating
2. Dip-Coating
One of the easiest and most common methods for producing thin films from a wide
range One of the easiest
of inorganic, hybrid,andand
most common methods
nanocomposite for is
materials producing
the sol–gel thin films [24–26].
method from a wide
range of inorganic, hybrid, and nanocomposite materials is the
Considering that it provides for coating a broad range of substrates and complicated sol–gel method [24–26].
geometries, including substrates with holes or intricate patterns, it provides for a high ge-
Considering that it provides for coating a broad range of substrates and complicated
ometries,
degree including
of control over substrates with holes and
the crucial parameters or intricate patterns,
offers flexibility it cannot
that provides for a high de-
be achieved
greeother
with of control overprocesses.
traditional the crucialThere
parameters andways
are several offers
forflexibility
wet thin-filmthatcoating,
cannotnamely,
be achieved
dip-coating [27,28], spin-coating [29], spray-coating [30], and flow-coating
with other traditional processes. There are several ways for wet thin-film coating, namely, [31], among
others. Fundamentally,
dip-coating the substrate[29],
[27,28], spin-coating to bespray-coating
coated is submerged in the
[30], and initial solution
flow-coating and
[31], among
then pulled
others. out at a consistent
Fundamentally, withdrawal
the substrate speed
to be during
coated the process,in
is submerged which is carried
the initial out and
solution
under well-measured
then pulled out at a temperature and air conditions.
consistent withdrawal A fine-tuning
speed during of the film
the process, which properties,
is carried out
including thickness, optical constants, and interior structure, is
under well-measured temperature and air conditions. A fine-tuning of the filmmade feasible by precisely
properties,
controlling the withdrawal rate and evaporation circumstances. The solution uniformly
including thickness, optical constants, and interior structure, is made feasible by precisely
spreads out along the surface of the substrate because of the collective effects of viscous
controlling the withdrawal rate and evaporation circumstances. The solution uniformly
drag and capillary action. Evaporation takes place at the process’ last stage, resulting in the
spreadsofout
gelation thealong thecoated
film. The surface of the substrate
substrates because
often receive of the treatment,
a post-heat collectivewhich
effectsaffects
of viscous
drag
the and capillary
properties action.
of the films Evaporation
[32]. takesprocess
The dip-coating place at the process’
is shown in Figurelast2.stage, resulting in
the gelation of the film. The coated substrates often receive a post-heat treatment, which
affects the properties of the films [32]. The dip-coating process is shown in Figure 2.
Coatings 2022,
Coatings 12,12,
2022, x FOR
1115 PEER REVIEW 4 of 22 4 of

Figure 2.2.Sequential
Figure Sequentialstages of the
stages sol–gel
of the dip-coating
sol–gel method
dip-coating for thinfor
method filmthin
deposition: Stage 1—the
film deposition: Stage 1—th
substrate is dipped and immersed in the sol precursor, Stage 2—the substrate is
substrate is dipped and immersed in the sol precursor, Stage 2—the substrate is withdrawn withdrawn at a at
steady rate, Stage 3—solvent evaporation produces the gelation of the
steady rate, Stage 3—solvent evaporation produces the gelation of the layer.layer.

The effectiveness of the dip-coating process can be directly impacted by several factors,
The effectiveness of the dip-coating process can be directly impacted by several fa
such as pH and solution concentration, by changing, for example, its viscosity. However,
tors, such as pHstudies
as contemporary and solution
employconcentration,
coating procedures by changing, for example,
that have already its viscosity. How
been documented
ever, as contemporary
in earlier works, most authors studies don’temploy
talk muchcoating
aboutprocedures
pH and solutionthat have already
viscosity. Fewer been docu
mented
repetitions of the dip-coating process are required to produce a certain thickness or amountviscosit
in earlier works, most authors don’t talk much about pH and solution
Fewer repetitions
of deposited of the
mass when dip-coating
using more viscous process are required
solutions since theyto produce
lead a certain
to greater agglomer- thickness o
ation and thicker layers of coating [33]. However, the resultant
amount of deposited mass when using more viscous solutions since they lead to great coating could potentially
break and clump particles
agglomeration and thickerin undesirable
layers ofplaces.
coating To obtain past these issues,
[33]. However, the dip-coating
the resultant coating cou
technique can provide a more homogenous coating by using a less viscous solution in
potentially break and clump particles in undesirable places. To obtain past these issue
combination with multiple repeats. The structure’s rate of immersion in the solution is yet
the dip-coating
another factor that technique canthe
might affect provide
coating’sa more homogenous
features [34]. A highcoating by using a for
rate of immersion, less viscou
solution
example, may in combination
produce thickerwith multiple
layers because repeats. The structure’s
the solution’s viscous forces rateareofincreased,
immersion in th
solution is yetaccumulation
causing greater another factor thatstructure’s
on the might affect the[35].
surface coating’s features [34]. A high rate
immersion,
For thin-filmfor example, may produce
coating techniques thicker layers
to be employed because
successfully the solution’s
in integrated optics,viscous
the forc
film thickness must be completely under control. Because
are increased, causing greater accumulation on the structure’s surface [35]. of this, thickness control is impor-
tant for
Forallthin-film
thin-film coating
development methods,
techniques toincluding sol–gel.
be employed It has been reported
successfully that theoptics, th
in integrated
coating speed, angle of inclination, and sol concentration have a major role in determining
film thickness must be completely under control. Because of this, thickness control is im
the ultimate thickness [36–38]. In addition, the ultimate heat-treated thickness can also be
portant
influenced forby allthe
thin-film development
sol viscosity, density, and methods, including
liquid-vapor surfacesol–gel.
tension It hasInbeen
[39]. [40],reported
it is th
the coating
stated speed, angle
that a cleanroom of inclination,
atmosphere is required and
for sol concentration
the coating procedure have a major
to produce role in dete
sol–gel
mining
thin filmsthe with ultimate thickness
great optical quality. [36–38].
To produceIn addition, the ultimate
organic dye-doped thin heat-treated
films with tailoredthickness ca
porosity
also for use in chemical
be influenced by the solsensing and optoelectronics,
viscosity, density, and aliquid-vapor
three-step sol–gel procedure
surface tension [39]. I
was developed
[40], it is stated[41]. thatAdditionally,
a cleanroom ceramic films generated
atmosphere fromfor
is required sol–gel are also presented
the coating procedure to pr
in [24]. Here are some further important papers on
duce sol–gel thin films with great optical quality. To produce organicthe sol–gel technique [42–51]. dye-doped th
Silica, titania, and silica-titania materials produced by the sol–gel technique have all
films with tailored porosity for use in chemical sensing and optoelectronics, a three-ste
undergone extensive research due to their potential optical uses [52–57]. The early part of
sol–gel
the 1980sprocedure was developed
saw the beginning of their use [41].
in Additionally,
the production ceramic films generated
of silica-titania WG films. The from sol–g
are also presented in [24]. Here are some further important
first individuals to do so were Herrmann and Wildman. However, they used MERCK’s [53] papers on the sol–gel tech
nique [42–51].
commercially available liquid-coat solutions rather than synthetic sols. The research team
led by Lukosz
Silica, produced
titania, and planar evanescent
silica-titania WG chemical/biochemical
materials produced by the sol–gel sensorstechnique
utilizing have a
these WG films, which were coated on glass substrates using the
undergone extensive research due to their potential optical uses [52–57]. The early part dip-coating technique
and 1980s
the had refractive
saw thenbeginning
= 1.8 at λ =of612.5
theirµm use [54–56,58]. These filmsofhave
in the production optical losses
silica-titania WGoffilms. Th
2.5 dB/cm for λ = 632.8 µm [58]. Spin-coating was used by Jiwei et al. to fabricate SiO2 -TiO2
first individuals to do so were Herrmann and Wildman. However, they used MERCK
WG films that were then coated on SiO2 /Si (111) substrates [57]. The greatest refractive
[53] commercially available liquid-coat solutions rather than synthetic sols. The researc
team led by Lukosz produced planar evanescent WG chemical/biochemical sensors utili
ing these WG films, which were coated on glass substrates using the dip-coating techniqu
and had refractive n = 1.8 at λ = 612.5 μm [54–56,58]. These films have optical losses of 2
dB/cm for λ = 632.8 μm [58]. Spin-coating was used by Jiwei et al. to fabricate SiO2-TiO
Coatings 2022, 12, x FOR PEER REVIEW 5 of 23

Coatings 2022, 12, 1115 5 of 22

of 7.4 dB/cm. It should be noted that 750 °C annealing temperatures were used to generate
such a high refractive index value. The phase change from anatase to rutile is expected to
index of the films was n = 1.87 at λ = 632.8 µm, yet they had very significant optical losses
occur
of at suchIthigh
7.4 dB/cm. should temperatures,
be noted thatmaking WG filmstemperatures
750 ◦ C annealing much morewere lossy. There
used are also other
to generate
studies [59–62] reporting the creation and characterization
such a high refractive index value. The phase change from anatase to rutile is expected of composite SiO 2-TiO2 films,
to
although
occur at suchtheir
high waveguiding
temperatures, characteristics
making WG films weremuch not studied.
more lossy. There are also other
studies If [59–62]
the titania concentration
reporting the creation is greater than 20 wt.%,ofthe
and characterization sol–gel-based
composite SiO2 -TiOmanufacturing
2 films,
process of
although SiOwaveguiding
their 2-TiO2 is quite challenging.were
characteristics Thisnotis studied.
due to titania’s great propensity to crys-
If the
tallize andtitania
produce concentration is greater
distinct phases. Asthan 20 wt.%,
a result, the sol–gel-based
manufactured films manufacturing
exhibit large optical
process
losses and of SiOare2 -TiO is quite challenging.
not 2amorphous [63]. Another This issue
is duethat to titania’s great propensity
causes optical losses to to increase
crystallize and produce distinct phases. As a result, manufactured
over time is long-term stability [64]. These challenges were overcome by Karasinski et al. films exhibit large optical
losses and are
by creating SiOnot amorphous [63]. Another issue that causes optical losses to increase
2-TiO2 WG films with a 50% weight TiO2 content that are low-loss and long-
over time is long-term stability [64]. These challenges were overcome by Karasinski et al.
term stable [23]. Using the dip-coating process on BK7 glass substrates, silica-titanium WG
by creating SiO2 -TiO2 WG films with a 50% weight TiO2 content that are low-loss and
layers with a SiO2-TiO2 = 1:1 molar ratio were created, which were subsequently heated to
long-term stable [23]. Using the dip-coating process on BK7 glass substrates, silica-titanium
500 °C. Thewith
WG layers primary
a SiO2chemical
-TiO2 = 1:1 precursors
molar ratio forwere
silicacreated,
SiO2 and titania
which TiOsubsequently
were 2 are tetraethyl or-

thosilicate
heated to 500Si (OC
◦ C. The2H5)4 (TEOS) and tetraethyl orthotitanate Ti (OC2H5)4 (TET), respectively.
primary chemical precursors for silica SiO2 and titania TiO2 are
tetraethyl orthosilicate hydrochloric
Water, ethanol, and Si (OC2 H5 )4 (TEOS)acid (HCl), which catalyzes
and tetraethyl orthotitanate the Tiprocesses
(OC2 H5 )4of(TET),
condensa-
tion and hydrolysis,
respectively. Water, ethanol,are theandadditional
hydrochloric substances
acid (HCl), used in the
which procedure.
catalyzes the processes of
Moreover,
condensation andKarasinski
hydrolysis,and are theco-workers
additionalproduced
substances a variety
used in of thefilms on glass substrates
procedure.
Moreover, Karasinski and co-workers produced a variety
at various speeds to identify the key technical characteristic that demonstrates of films on glass substratesthe link
at various speeds to identify the key technical characteristic
between the thickness and refractive index of waveguide films about the speed that demonstrates the linkof sub-
between the thickness
strate removal fromand therefractive
sol. After index of waveguide
deposition, films about
the films underwentthe speed of substrate
a 60-min annealing
removal from the sol. After deposition, the films underwent a
process at 500 °C. Finally, using the monochromatic, multiangle ellipsometer Sentech SE 60-min annealing process
at 500 ◦ C. Finally, using the monochromatic, multiangle ellipsometer Sentech SE 400 adv
400 adv with a wavelength of 632.8 nm, the thickness and refractive index of those films
with a wavelength of 632.8 nm, the thickness and refractive index of those films were
were determined. Figure 3 displays the outcomes’ features [36]. From the parameters
determined. Figure 3 displays the outcomes’ features [36]. From the parameters shown
shown
in Figurein3,Figure
a single3,coating
a single coating can
procedure procedure can only
only provide providethickness
a maximum a maximum thickness of
of roughly
roughly
230 nm in the230range
nm in the range of
of withdrawal withdrawal
speed shown. With speed shown. coating
the repeated With the repeated
method, thickercoating
method,
films maythicker films
be created, may is
which beimportant
created, which
because is the
important
sample because
needs to the sample needs
be annealed after to be
annealed
each coating.afterIneach
order coating. In order
to determine thetoproperties
determineshown the properties
in Figureshown 3 of theinsetFigure
of ten3 of the
set 2of
SiO ten2 waveguides
-TiO SiO2-TiO2 waveguides that were
that were created created
for this research for in
this research
a single in a procedure,
coating single coating as pro-
well as a as
cedure, fewwell
more asfilms
a fewinmore
a doublefilmscoating process.
in a double coating process.

Figure3.3.The
Figure Theexperimentally determined
experimentally characteristic
determined of waveguide
characteristic film thickness
of waveguide and refractive
film thickness and refractive
index against change in substrate withdrawal speed from the sol [36].
index against change in substrate withdrawal speed from the sol [36].

Nanoimprint lithography (NIL) is used to construct a Bragg grating (BG) device in a

Nanoimprint lithography (NIL) is used to construct a Bragg grating (BG) device in a
sol–gel silica WG for bio-photonic applications [65]. A reasonably wide area in the range
sol–gel silica WG for bio-photonic applications [65]. A reasonably wide area in the range
of several micrometers with a resolution in the order of several nanometers is achieved by
the procedure, which also achieves non-standardized lithography in sol–gel silica at a
 Coatings 2022, 12, 1115 6 of 22

Coatings 2022, 12, x FOR PEER REVIEW 6 of 23

of several micrometers with a resolution in the order of several nanometers is achieved

by the procedure, which also achieves non-standardized lithography in sol–gel silica at
ahigh
highresolution. In aa sol–gel
resolution. In sol–gelsilica
silicaoptical
opticalWG,WG, structures
structures withwith between
between 250 90
250 and andnm90 nm
resolutions were shown for a sizable area that has not yet been tuned. For a 1 mm long long
resolutions were shown for a sizable area that has not yet been tuned. For a 1 mm
region,aa250
region, 250nmnmperiodic
periodic structure
structure BGBG is produced.
is produced. TwoTwo sol–gel
sol–gel silicasilica BG structures,
BG structures, one one
measuring250
measuring 250nm
nmbroad
broad andand
thethe other
other 90 nm
90 nm wide,
wide, werewere
thenthen photographed
photographed usingusing
SEM SEM
asshown
as shownininFigure
Figure 4a,b.
4a,b. TheThe transmission
transmission andand reflection
reflection spectra
spectra ofBG
of the thestructure
BG structure
are are
presentedininFigure
presented Figure 4c,d,
4c,d, respectively.
respectively. Based
Based on the
on the transmission
transmission and reflection
and reflection spectra
spectra of of
laser
laserlight
lightcoupled
coupledinto
intothe WG
the WGat aatwavelength
a wavelength of 1.55 µm,μm,
of 1.55 the efficiency of theofgrating
the efficiency the grating
structure
structureininthe
theWG
WG waswasevaluated.
evaluated. TheThe
transmission
transmissionand and
reflection spectra
reflection demonstrate
spectra demonstrate
that the WG grating was successfully constructed using the NIL
that the WG grating was successfully constructed using the NIL procedure. procedure.

Figure4.4.Sol–gel
Figure Sol–gelsilica
silica BG,
BG, (a)(a)
SEMSEM image
image of the
of the large
large areaarea of periodic
of periodic structure
structure [65],
[65], (b) (b) zoomed
zoomed
area of the periodic structure [65], (c) transmission spectrum of the BG structure [65], (d)
area of the periodic structure [65], (c) transmission spectrum of the BG structure [65], (d) reflection reflection
spectrum of the BG structure
spectrum of the BG structure [65]. [65].

3.3.Spin-Coating
Spin-Coating
Spin-coating
Spin-coatingisisa common
a common method
method for for
producing
producing uniform coatings
uniform of theofnecessary
coatings the necessary
thickness; unfortunately, because spin-coating wastes resources at a rate of more than
thickness; unfortunately, because spin-coating wastes resources at a rate of more than
90%, materials prices increase as the film-coated area grows [66]. Since many years ago,
90%, materials prices increase as the film-coated area grows [66]. Since many years ago,
thin films have been deposited via spin-coating. In this method, a tiny drop of coating
thin films
material have
is put intobeen depositedcenter
the substrate’s via spin-coating. In thisismethod,
before the substrate rotated ata atiny drop of
regulated highcoating
speed. The substrate spins during the spin-coating process around an axis that must be high
material is put into the substrate’s center before the substrate is rotated at a regulated
speed. to
parallel The thesubstrate
region to spins during
be coated. the spin-coating
Consequently, processfilm
a thin coating around
formsanonaxis
the that must be
surface
parallel to the region to be coated. Consequently, a thin coating film forms
as the coating material is distributed toward and finally moves away from the substrate’s on the surface
as theThe
edge. coating
kind material
of coatingis(viscosity,
distributed toward
drying and
rate, finally surface
% solids, moves tension,
away from etc.)the substrate’s
and the
edge.
spin The kindconditions,
processing of coatingsuch(viscosity, drying
as rotation rate,
speed, will%determine
solids, surface tension,
the final etc.) and the
film thickness
and
spinother attributes.
processing The stages
conditions, of as
such therotation
spin-coating
speed, process are shownthe
will determine in final
Figure 5. The
film thickness
size of the substrate is one of the key drawbacks of spin-coating. High-speed
and other attributes. The stages of the spin-coating process are shown in Figure 5. The spinning is size
of the substrate is one of the key drawbacks of spin-coating. High-speed spinning is more
challenging as the size goes up since film thinning gets more challenging. There is practi-
cally limited material efficiency in spin-coating. In general, throughout the process, 95%–
98% of the material is thrown off and discarded, and only 2%–5% of the material is dis-
 Coatings 2022, 12, 1115 7 of 22

more challenging as the size goes up since film thinning gets more challenging. There is
practically limited material efficiency in spin-coating. In general, throughout the process,
Coatings 2022, 12, x FOR PEER REVIEW 7 of 23
95%–98% of the material is thrown off and discarded, and only 2%–5% of the material is
dispensed onto the substrate.

Figure 5. Stages
Figure of spin-coating
5. Stages of spin-coatingofofthin-film on aa substrate.
thin-film on substrate.Step
Step1:1:Solution
Solution is deposited
is deposited on the
on the
substrate. Step
substrate. 2: 2:
Step Rotational
Rotationalspread outofofthe
spread out the solution.
solution. StepStep 3: Evaporation
3: Evaporation of the solvent.
of the solvent.

To To change the solid loading, viscosity, and volatility of the coating solution using this
change the solid loading, viscosity, and volatility of the coating solution using this
approach, several organic additives are frequently used. This technique is very well adapted
approach, several organic additives are frequently used. This technique is very wel
to create an ultrathin film on different substrates. In 1958, Emslie and colleagues suggested
adapted to create an
the spin-coating ultrathin
process model film on the
forecast different substrates.
film thickness In 1958,
as a function of Emslie and colleagues
specific physical
suggested
parameters. The dip-coating parameters can be correlated using this method, though [67]. of spe
the spin-coating process model forecast the film thickness as a function
cificHuang
physicaland Chou further claimed,
parameters. The based on this function,
dip-coating parametersthat the can
solution’s viscosity greatly
be correlated using this
depends on the shear rate because viscosity is linked to the
method, though [67]. Huang and Chou further claimed, based on this function, that theshear stress. Theoretically, the
shear forces caused by viscosity and solution spinning mostly influence the membrane
solution’s viscosity greatly depends on the shear rate because viscosity is linked to the
thickness. A thinner, yet more homogeneous membrane would be produced by the spin-
shear stress.
coating Theoretically,
process’ less viscousthe shear forces
precursor solutioncaused by viscosity
[68]. Burmann and solution
et al. showed that whilespinning
mostly influence
the solvent the membrane
evaporation thickness.when
effect is important A thinner,
employing yetspin-coating
more homogeneous for membrane membrane
would be produced by the spin-coating process’ less viscous precursor
casting, the rotational duration had little impact on membrane thickness. Nevertheless, the solution [68]. Bur
mann quick solvent
et al. evaporation
showed might
that while theresult in membranes
solvent evaporation that are unreliable
effect and fragile
is important when[69].employ
Self-supporting ultrathin TiO films were disclosed by Hashizume
ing spin-coating for membrane casting, the rotational duration had little impact
2 and Kunitake using theon mem
spin-coating method [70]. The spin-coating method was used to create the ultrathin layer
brane thickness. Nevertheless, the quick solvent evaporation might result in membranes
of polyvinyl alcohol (PVA), which was then coated with titanium tetrabutoxide. The self-
thatsupporting
are unreliable andPVA/titanium
ultrathin fragile [69]. Self-supporting
composite film was ultrathin
eventually TiO 2 films were disclosed by
created by dissolving
Hashizume
the soluble and Kunitake
polymer. using the
Spin-coating spin-coating
is frequently method
employed [70].toThe
in labs spin-coating
create small-sized method
was used to create the ultrathin layer of polyvinyl alcohol (PVA), which
membranes, but the technique is not appropriate for producing photocatalytic was then coated
membranes
withontitanium
a large scale to be used in practical
tetrabutoxide. applications. ultrathin PVA/titanium composite film
The self-supporting
Due to defects
was eventually created in the thin films that
by dissolving themakesolubleup organic
polymer. solar cells, they areistypically
Spin-coating frequently em
not repeatable. Wet spun-on PEDOT:PSS films are subjected to an imposed ultrasonic
ployed in labs to create small-sized membranes, but the technique is not appropriate fo
substrate vibration post-treatment to reduce the density of pinholes and defects in PEDOT:
producing
PSS, which photocatalytic membranes
is the hole transporting onofa alarge
layer scalepolymer
standard to be used solarincell,
practical applications
consisting of
Due to defects in the thin films that make
glass/ITO/PEDOT:PSS/P3HT:PCBM/Al, and to up organic
reduce solarincells,
scattering device they are typically no
performance
repeatable.
(SVPT) [71]. WetThespun-on PEDOT:PSS
forced vibration enhances films
the wetarespun-on
subjected films’tomixing
an imposed ultrasonic sub
and homogeneity,
which
strate in turn post-treatment
vibration advances the nanostructure
to reduce of thethedensity
resulting ofthin solid films.
pinholes and The average
defects in PEDOT
power conversion efficiency (PCE) of 14 identical cells rises by 25% when the SVPT, a
PSS, which is the hole transporting layer of a standard polymer solar cell, consisting o
mechanical, one-step, and low-cost technique, is used, and the standard deviation drops by
glass/ITO/PEDOT:PSS/P3HT:PCBM/Al, and to reduce scattering in device performance
22%, showing that the device’s photovoltaic performance is greatly enhanced and becomes
(SVPT) [71]. The forced vibration enhances
more consistent. This does away with various time-consuming, the wet spun-on films’
costly mixing
chemical andand homogene
thermal
ity, processes
which in that turnareadvances
typicallythe
used nanostructure
to increase cellof the resulting
repeatability [71].thin
Thesolid films. The
representation of average
the whole device and a cross-section of a cell that was photographed
power conversion efficiency (PCE) of 14 identical cells rises by 25% when the SVPT, a using an SEM are
shown in Figure
mechanical, 6a,b, and
one-step, respectively.
low-cost Thetechnique,
cross-sectional SEM picture
is used, and the in Figure
standard 6b shows that drops
deviation
the PEDOT:PSS film has a thickness of roughly 40 nm when the spin rotation is adjusted
by 22%, showing that the device’s photovoltaic performance is greatly enhanced and be
comes more consistent. This does away with various time-consuming, costly chemical and
thermal processes that are typically used to increase cell repeatability [71]. The represen
tation of the whole device and a cross-section of a cell that was photographed using an
 Coatings 2022, 12, 1115 8 of 22

to 5000 rpm. It is calculated that the PEDOT:PSS film thickness produced at 3000 and
Coatings 2022, 12, x FOR PEER REVIEW 8 of 23
4000 rpm is 52 and 45 nm, respectively. The film was dried at 120 ◦ C for 30 min after the
PEDOT:PSS solution was deposited, whether with or without ultrasonic vibrations [71].

Figure 6. 6.
Figure Films deposited
Films depositedvia
viaspin-coating
spin-coating method (a)Graphical
method (a) Graphicalillustration
illustration
of of
thethe solar
solar cellcell [71],
[71],
(b)(b)
SEMSEMcross-sectional
cross-sectionalimage of aacell
image of cell[71].
[71].

4. Roll-Coating
4. Roll-Coating
Roll-coating is a pre-metered coating that applies coating liquid to a substrate using a
Roll-coating is a pre-metered coating that applies coating liquid to a substrate using
succession of rollers. The amount of coating material provided to the substrate is practically
a succession
independentofofrollers. The amount
the characteristics andof coatingofmaterial
structures the fabricprovided
because a to the substrate
metered layer of the is prac-
tically
coatingindependent
liquid is firstofgenerated
the characteristics
on the rollerand structures
surface before it isoftransferred
the fabric tobecause a metered
the substrate.
layer of the coating liquid is first generated on the roller surface
Precise control is achievable and is mainly governed by the rheology of the fluid and the before it is transferred to
therelative
substrate.
speed Precise
of two control
spinningissurfaces.
achievable and revolving
A single is mainlyrollergovernedis usedby inthe
the rheology
most basicof the
roll-coating
fluid and the setup.
relative Thespeed
roller’s
ofupper portion is surfaces.
two spinning in touch with the substrate,
A single revolving while its lower
roller is used in
half is submerged in a coating liquid bath. A portion of the liquid
the most basic roll-coating setup. The roller’s upper portion is in touch with the substrate, film formed by the
coating liquid on the roller surface is transferred from the
while its lower half is submerged in a coating liquid bath. A portion of the liquid roller surface to a substrate as film
the roller rotates. Hydrodynamics controls the quantity of coating that is applied to the
formed by the coating liquid on the roller surface is transferred from the roller surface to
substrate. The elements affecting coating thickness include substrate speed, roller rotation
a substrate as the roller rotates. Hydrodynamics controls the quantity of coating that is
speed, and the rheological characteristics of the coating fluid. One roller serves as both
applied to theand
a metering substrate. The elements
an application device inaffecting coating thickness
this configuration. By adding include
additionalsubstraterollers,speed,
roller rotation speed, and the
more accurate control is made possible. rheological characteristics of the coating fluid. One roller
serves as both a metering
A metering roller, an and an application
applicator roller, and device
a backup inroller
this configuration.
are all used in a By adding ad-
three-roll
coating. Nip feed coating and L-head
ditional rollers, more accurate control is made possible. coating are typical three-roll arrangements. In
three-roll nip feed coating, the nip created by a metering roller and
A metering roller, an applicator roller, and a backup roller are all used in a three-roll an applicator roller
serves
coating. Nip as a feed
reservoir and and
coating is inundated with coating
L-head coating liquid.three-roll
are typical The metering roller rotatesIninthree-
arrangements.
the opposite direction to the applicator roller and measures the amount of coating liquid
roll nip feed coating, the nip created by a metering roller and an applicator roller serves
transferred to the substrate once the applicator roller picks up the coating liquid from the
as nip.
a reservoir and is inundated with coating liquid. The metering roller rotates in the op-
Any coating liquid that remains on the metering roller surface after the coating liquid
posite
passes from thetometering
direction the applicator
roller toroller and measures
the applicator roller isthe amount
cleaned with ofacoating
doctor blade liquidtotrans-
ferred
preventto the substrate
coating defectsonce
suchthe applicator
as streaks roller
or rough picks
film. up theroller
A backup coating liquid
supports thefrom
film the
as nip.
Anyit iscoating
deposited liquid
onto that remainssurface
the substrate on thefrom metering roller surface
the applicator after thethis
roller. Although coating
designliquid
passes
only from
requiresthea metering
small amount roller to the applicator
of coating fluid, it tendsroller is cleaned
to leak. with aliquid
When coating doctor hasblade
a to
low viscosity,
prevent coatingit defects
might besuchdifficult. A liquidorfilm
as streaks is created
rough film. onA the applicator/dipping
backup roller supports roller
the film
as revolving through
it is deposited the coating
onto liquid in
the substrate a three-roll
surface frompan thefeed or L-headroller.
applicator coating, metered by
Although this de-
a metering roller, and coated on the substrate fabric on a backup roller as shown in Figure 7.
sign only requires a small amount of coating fluid, it tends to leak. When coating liquid
A fourth roller—a pick-up roller operating at a slower speed—can be installed to boost
has a low viscosity, it might be difficult. A liquid film is created on the applicator/dipping
coating speed. This method is known as a four-roll pan-fed coating system. Since the
roller revolving
applicator throughrollers
and metering the coating
rotate in liquid in adirections,
opposite three-rollthe pan feed or L-head
configurations in the coating,
figure me-
tered
are by a metering
referred roller, metering.
to as reverse and coated on themetering
Forward substrateisfabricthe term on used
a backupwhenroller as shown
they both
in Figure 7.
rotate in the same direction. Forward roll metering usually produces unstable, non-uniform
films, whereas reverse metering generates smoother, more stable films. As a result, reverse
roll coating is increasingly frequently employed. Hot melts, solvent-based coatings, and
water-based solutions can all be used for roller coating. Hot melt roller coating involves
 Coatings 2022, 12, 1115 9 of 22

Coatings 2022, 12, x FOR PEER REVIEW

melting solid pellets between hot melt rollers, creating a melt film, and then depositing the9 of 23
melt film on a substrate. Typically, hot melt is applied after preheating the substrate.

Figure7.7.Roll-coating
Figure Roll-coating set-up.
set-up.

Under
A fourththe presumption
roller—a pick-up of a small rolloperating
roller curvature, at Greener
a slowerand speed—can
Middleman performed
be installed to
the theoretical study on roll-coating and examined the scenario
boost coating speed. This method is known as a four-roll pan-fed coating system. where the roll and sheet Since
are moving at the same speed [14]. They were able to determine
the applicator and metering rollers rotate in opposite directions, the configurations the precise equation forin the
film thickness and pressure distribution for a Newtonian fluid under
figure are referred to as reverse metering. Forward metering is the term used when they the approximation
of lubrication. They quantitatively calculated film thickness, pressure, and roll-separating
both rotate in the same direction. Forward roll metering usually produces unstable, non-
force for viscoelastic and power-law fluids as well. The overall Navier-Stokes equations
uniform films, whereas reverse metering generates smoother, more stable films. As a re-
were solved by the finite element method by Coyle et al. [72]. They then examined the
sult, reverse roll
approximated coatingmodel’s
lubrication is increasingly
findings frequently
and concluded employed.
that it wasHoteffective
melts, solvent-based
only for
coatings, and water-based solutions can all be used
systems with large capillary numbers and low surface tension. Hintermaier for roller coating. Hot melt roller coat-
and White
used a lubricating scheme to study the flow of water between two rollers, and their and
ing involves melting solid pellets between hot melt rollers, creating a melt film, cal- then
depositing
culated the melt
techniques film on
closely a substrate.
matched Typically,
their reported hot melt is [73].
performance applied Theafter preheating
coating fluxes the
substrate.
for several non-Newtonian fluid models were both theoretically and empirically investi-
gatedUnder the presumption
by Benkreira of aSofou
et al. [74–77]. smallandrollMissoula
curvature, Greener
used the powerand Middleman performed
lubrication theory,
Bingham plastics,
the theoretical and Hershel-Bulkley
study on roll-coating models
and examinedto examinethe the roll-over-web
scenario where the coating flow sheet
roll and
computationally
are moving at the [78].
same speed [14]. They were able to determine the precise equation for
filmUtilizing
thicknessa and third-grade
pressure fluid lubrication
distribution forapproximation,
a Newtonian fluid Zahidunderet al. the
examined the
approximation
roll coating process and numerically evaluated all the crucial characteristics.
of lubrication. They quantitatively calculated film thickness, pressure, and roll-separating By assuming
that both the roller and the sheet are porous [79]. They also theoretically explored the
force for viscoelastic and power-law fluids as well. The overall Navier-Stokes equations
second-grade fluid roll coating method [80]. It is expected that the pace at which fluid
were solved by the finite element method by Coyle et al. [72]. They then examined the
enters the roller surface will be the same as the rate at which fluid exits the web surface.
approximated
With the supportlubrication model’s
of the lubrication findings andtheory,
approximation concluded
Ali et that it was effective
al. investigated the web-only for
systemsmethod
coating with large for acapillary
pair stress numbers
fluid [81].andThey lowalso
surface tension.
evaluated theHintermaier and White
pressure gradient,
pressure, velocity, roll-separating force, power input, and other crucial parameters. Bycalcu-
used a lubricating scheme to study the flow of water between two rollers, and their
lated techniques
bringing closely
the pair stress matched
constant their reported
to infinity, the findingsperformance
were compared [73]. The coating
to those fromfluxes
the for
several non-Newtonian
Newtonian fluid. To conduct fluid
an models were investigation
experimental both theoretically
of the and
forwardempirically
and reverseinvestigated
roll-
by Benkreira
coating processes et al. [74–77]. Sofou
in meniscus and Missoula
fluid mechanics, Gaskellused theadopted
et al. power lubrication theory, Bing-
an optical sectioning
technique [82]. To determine key parameters such as intake flow
ham plastics, and Hershel-Bulkley models to examine the roll-over-web coating flow com- rate, film thickness,
meniscus
putationallyposition,
[78]. and pressure field, several tests were carried out. Nevertheless, the
optimal homotopy asymptoticfluid
Utilizing a third-grade method (OHAM)approximation,
lubrication was not used to assess
Zahidthe impacts
et al. examinedof pair
the roll
stresses generated during the roll-over-web operation. A semi-analytical
coating process and numerically evaluated all the crucial characteristics. By assuming that approximation
method for solving non-linear problems is the OHAM [83]. In contrast to other methods
both the roller and the sheet are porous [79]. They also theoretically explored the second-
of perturbation, this methodology is independent of any big or small factors and offers a
grade fluid roll coating method [80]. It is expected that the pace at which fluid enters the
roller surface will be the same as the rate at which fluid exits the web surface. With the
support of the lubrication approximation theory, Ali et al. investigated the web-coating
method for a pair stress fluid [81]. They also evaluated the pressure gradient, pressure,
velocity, roll-separating force, power input, and other crucial parameters. By bringing the
pair stress constant to infinity, the findings were compared to those from the Newtonian
 stresses generated during the roll-over-web operation. A semi-analytical approximat
method for solving non-linear problems is the OHAM [83]. In contrast to other meth
of perturbation, this methodology is independent of any big or small factors and offe
suitable way to manage the convergence of the approximation solution and, if necessa
Coatings 2022, 12, 1115 10 of 22
modify the convergence zones.
A well-known and efficient method for making solar cells is roll-to-roll (R-2-R). A
ditionally, several film-forming techniques, including inkjet printing, vacuum depositi
suitable way to manage the convergence of the approximation solution and, if necessary,
doctor-blading, slot-die coating [84], and CVD, can be used in the production of R-2
modify the convergence zones.
Flexible substrates
A well-known andare required
efficient method for for
themaking
production of R-2-R
solar cells [85]. Figure
is roll-to-roll (R-2-R). 8aAd-depicts
PSCs’ R-2-R
ditionally, process
several [86]. The
film-forming substrateincluding
techniques, must also be printing,
inkjet able to maintain the technique’s r
vacuum deposition,
uisite temperature.
doctor-blading, slot-dieDue to their
coating [84],limited
and CVD,temperature
can be used range
in the(150–200
production °C)of[87], polyethyl
R-2-R.
Flexible substrates are required for the production of R-2-R [85].
terephthalate (PET) and polyethylene naphthalate (PEN) commonly employ flexible s Figure 8a depicts the
PSCs’ R-2-R
strates. process
At low [86]. The substrate
temperatures, Jung etmust also be able
al. produced to maintain
a device usingthe technique’s
flexible substrates w
requisite temperature. Due to their limited temperature range (150–200 ◦ C) [87], polyethy-
a promising PCE of 9.43% [88]. An R-2-R method with 4.9 percent PCE was created
lene terephthalate (PET) and polyethylene naphthalate (PEN) commonly employ flexible
Krebs andAt
substrates. colleagues. In the realm
low temperatures, Jung et ofal.
organic
producedphotovoltaics,
a device using they exploited
flexible the benefit
substrates
with a promising PCE of 9.43% [88]. An R-2-R method with 4.9 percent PCE was created by evalua
R-2-R in the eye of processing and charges over huge areas. Additionally, they
the creation
Krebs of R-2-R
and colleagues. compatible
In the processes
realm of organic based on
photovoltaics, theyone-step
exploited andthe two-step
benefits of perovsk
R-2-R in the eye of processing and charges over huge areas.
layer production. Typically, direct coating on substrates is performed Additionally, they evaluated
through print
the creation ofGravure
techniques. R-2-R compatible processes
printing offers based on method
an efficient one-step forandprinting
two-steppatterned
perovskitelayers w
layer production. Typically, direct coating on substrates is performed through printing
high throughput and rapid printing speeds. It may also make it possible to produce PS
techniques. Gravure printing offers an efficient method for printing patterned layers with
on flexible substrates at a low cost and on an industrial scale. Kim et al. proposed a g
high throughput and rapid printing speeds. It may also make it possible to produce PSCs
vure
on printing-based
flexible substrates at aR-2-R approach,
low cost and on an and all ofscale.
industrial the Kim
gravure-printed
et al. proposed devices
a gravureshowed
efficiency of 17.2%,
printing-based whereasand
R-2-R approach, theallpartially R-2-R exhibits
of the gravure-printed 9.7%showed
devices based on two-step manuf
an efficiency
turing
of 17.2%,of the perovskite
whereas the partially layer.
R-2-RFigure
exhibits8b,c
9.7%depicts
based onthe PbI2 roll
two-step printed and
manufacturing J-V curves
of the
perovskite
R-2-R [86]. layer. Figure 8b,c depicts the PbI 2 roll printed and J-V curves of R-2-R [86].

Figure8.8.PSC
Figure PSC manufacturing
manufacturing process,
process, (a) Schematic
(a) Schematic representation
representation of the R-2-Rof the
PSCR-2-R PSC manufactur
manufacturing
process.Optical
process. Opticalrepresentations
representations of films
of films wrapped
wrapped on rolls
on rolls (Inset)(Inset) [86],
[86], (b) (b) Picture
Picture of a PbIof a PbI2 roll p
2 roll
duced using
produced using the R-2-Rmethod.
the R-2-R method. (Inset)
(Inset) Illustrations
Illustrations of the of the perovskite
perovskite conversionconversion
of PbI2 andofthePbI2 and
MAPbI
MAPbI 3 roll
3 roll [86],
[86], (c) (c)
J-VJ-V curves
curves of printed
of printed PSCs printed
PSCs printed on rolls on
withrolls withHTLs
various various
[86]. HTLs [86].

5. Spray-Coating
Considering the abundance of paints and varnishes included in spray devices that can
be purchased in stores all over the world, the spray-coating technique may be one of the
most useful for covering surfaces [89]. It might be difficult, though, to find a sprayer and a
 Considering the abundance of paints and varnishes included in spray devices
can be purchased in stores all over the world, the spray-coating technique may be on
the most useful for covering surfaces [89]. It might be difficult, though, to find a spr
and a coating solution that work well together. There are also other variants of this pr
Coatings 2022, 12, 1115 11 of 22
dure, including spray-coating with plasma [90], thermal spray [91], and powder
among others. The traditional spray-coating method is still the most often reported
to its low
coating cost that
solution andwork
lack well
of specialized equipment,
together. There though.
are also other Some
variants equipment
of this procedure,is conne
to compressors for photocatalytic coating so that the solution
including spray-coating with plasma [90], thermal spray [91], and powder [92], exits at among
the desired sp
and pressure
others. [93]. Similar
The traditional to the dip-coating
spray-coating technique,
method is still the most theoftensolution
reportedmustdue tobeitscorrectly
low cost and lack of specialized equipment, though. Some equipment
pared before being loaded into the spray. The precursor solution employed by Montec is connected to
compressors for photocatalytic coating so that the solution exits at the desired speed and
et al. contained merely commercial TiO2 and ethanol at a ratio of 1:20 by mass, res
pressure [93]. Similar to the dip-coating technique, the solution must be correctly prepared
tively, and produced promising benefits after being applied to both steel and cer
before being loaded into the spray. The precursor solution employed by Montecchio et al.
plates onmerely
contained several occasions
commercial TiO[94]. Following the structure’s preparation or pretreatm
2 and ethanol at a ratio of 1:20 by mass, respectively, and
the coating
produced is carried
promising outafter
benefits using a spray,
being appliedand the steel
to both material is thenplates
and ceramic allowed to dry at a s
on several
occasions [94]. Following
ified temperature andthe structure’s
time. To obtainpreparation or pretreatment,
the appropriate the coating
thickness is carried
or catalyst mass, the t
out using a spray, and the material is then allowed to dry at a specified
nique can be performed numerous times. Figure 9 is a schematic illustration of the sptemperature and
time. To obtain the appropriate thickness or catalyst mass, the technique can be performed
coating method. In this process, zinc acetate dihydrate and methanol were used in a
numerous times. Figure 9 is a schematic illustration of the spray-coating method. In this
trasoniczinc
process, spray pyrolysis
acetate dihydrate process by Bousmaha
and methanol were used et in
al.antoultrasonic
coat ZnOspray in apyrolysis
glass tube [95].
methylene
process blue dyeetcompletely
by Bousmaha al. to coat degraded during
ZnO in a glass tubephotocatalytic
[95]. The methylene experiments,
blue dye and the
entists claim
completely that this
degraded method
during is the best
photocatalytic for creating
experiments, and thethin layersclaim
scientists on flat
thatsurfaces
this suc
method
glass. is the best for creating thin layers on flat surfaces such as glass.

Figure9.9.Spray-coating
Figure Spray-coating process.
process.

A fine aerosol is created by forcing printing ink through a nozzle during the spray-
A fine aerosol is created by forcing printing ink through a nozzle during the sp
painting process. PSC’s typical performance in a spray coating method is constrained
painting
by process.isolated
issues including PSC’s typical
droplets,performance
a non-uniforminsurface,
a spray andcoating method
pinholes. is constraine
The distance
issues including isolated droplets, a non-uniform surface, and pinholes.
between the sample and the airbrush, the flow rate, the pressure, the substrate temperature, The distanc
tween
the the sample
concentration andblend
of the the airbrush,
solution, the theduration
flow rate, thespray,
of the pressure, the substrate
the cosolvent mixture, tempera
and the number of times the substrate is sprayed are just a few of the
the concentration of the blend solution, the duration of the spray, the cosolvent mixprocess variables for
spray
and thecoating that have
number been the
of times extensively
substrate studied.
is sprayed are just a few of the process variable
With a cell size of 2.5 cm2 , the greatest PCE observed is 4.1%. The polymer active
spray coating that have been extensively studied.
layer was prepared using mixed solvents, and the substrate was also heated to 40 ◦ C. It has
With athat
been shown cell size of 2.5
decreasing PCEcm
2, the greatest PCE observed is 4.1%. The polymer a
results in a scaling up of the cell area [96]. According to
layer was
research prepared
by Park using
et al. [97] mixed
and Kang solvents,
et al. [20], the and
PCE ofthethesubstrate was also
devices decreased as heated
the cell to 40 °
has increased.
area been shown Thethat
highdecreasing
sheet resistancePCEofresults in a scaling
the transparent up ofand
electrode thethe
cell area [96]. Accor
challenging
tuning of the large-area deposition process are to blame for this.
to research by Park et al. [97] and Kang et al. [20], the PCE of the devices decreased a
cell In studies
area on photoelectric
increased. The high devices,
sheetthe ultrasonicofspray
resistance the coating processelectrode
transparent (USCP) has and the c
proven appealing due to its high material efficiency, cheap manufacturing costs, and
lenging tuning of the large-area deposition process are to blame for this.
suitability to simplify production. Surface tension in the solvent, though, continues to be a
major In studies
barrier on photoelectric
to USCP’s devices,
ability to produce a smooth theorganic
ultrasonic spray
layer for coating
OLEDs. process (USCP
By integrating
proven appealing due to its high material efficiency, cheap manufacturing
an extra-low surface tension diluent and a surface tension control mechanism, a high-quality costs, and
ability to
polymer simplify
anode buffer production.
layer and a tiny Surface
molecule tension
emissioninlayer
the are
solvent, though,
effectively continues
achieved by to
 major barrier to USCP’s ability to produce a smooth organic layer for OLEDs. By integrat-
ing an extra-low surface tension diluent and a surface tension control mechanism, a high-
Coatings 2022, 12, 1115 quality polymer anode buffer layer and a tiny molecule emission layer are12effectively of 22

achieved by USCP [98]. Poly (3,4-ethylene dioxythiophene) polystyrene sulfonate (PE-

DOT:PSS) films benefit from the addition of low surface tension methyl alcohol because
USCP [98].clear
it causes Polyphase
(3,4-ethylene
separation dioxythiophene)
and increasespolystyrene
conductivity. sulfonate (PEDOT:PSS)
Additionally, a surfacefilmstension
benefit from the addition of low surface tension methyl alcohol because
control technique is provided to remove the influence of surface tension during the sol- it causes clear phase
separation and increases
vent evaporation stage conductivity.
of ultrasonicAdditionally,
spray coating a surface
the film. tension control technique is
provided to remove the influence of surface tension
A two-step sequential deposition method is used to construct during the solventmethylammonium
evaporation stage lead
of ultrasonic spray coating the film.
iodide PSCs using simple coating processes such as spray coating and drop-casting [99].
A two-step sequential deposition method is used to construct methylammonium lead
In the first stage, spray coating replaces the often-used lab-scale spin-coating for the dep-
iodide PSCs using simple coating processes such as spray coating and drop-casting [99]. In
osition
the of the
first stage, leadcoating
spray iodide, whilethe
replaces theoften-used
operatinglab-scale
variables of the former
spin-coating for the process
deposition are im-
of the lead iodide, while the operating variables of the former process are improved to sec-
proved to produce a completely coated and homogeneous sheet of lead iodide. In the
ond phase,
produce the touch-free
a completely coated drop-casting
and homogeneous and scalable pulsed-spray
sheet of lead iodide. In thecoating
secondsubstitute
phase, the
dip-coating
the touch-freeprocedure
drop-casting to deposit methylammonium
and scalable pulsed-spray coatingiodidesubstitute
on top of the lead iodide layer
the dip-coating
to create atomethylammonium
procedure deposit methylammonium lead iodide perovskite.
iodide on top ofItthe haslead
been discovered
iodide layer tothat
createthe effi-
aciency of perovskite films and devices created using pulsed-spray coating and drop-cast-
methylammonium lead iodide perovskite. It has been discovered that the efficiency
of
ingperovskite
is comparablefilms and devices
to those created
created using
using pulsed-spray
dip-coating andcoating andmethods,
that these drop-casting along is with
comparable
drop-casting’s to those created using
low material dip-coating
requirements, andthe
have thatpotential
these methods,
to takealong withof
the place drop-
dip-coat-
casting’s
ing in the low material requirements,
production of PSCs on ahave largethe potential
scale. to take the
Spray-drop andplace of dip-coating
spin-drop processes in were
the
used to create the winning devices, which showed power conversion efficienciestoof 6.92
production of PSCs on a large scale. Spray-drop and spin-drop processes were used
create the winning devices, which showed power conversion efficiencies of 6.92 percent
percent and 9.48 percent, respectively. Higher efficiencies are anticipated because of ap-
and 9.48 percent, respectively. Higher efficiencies are anticipated because of applying the
plying the improved characteristics and additional layers when fabricating devices in a
improved characteristics and additional layers when fabricating devices in a low-humidity
low-humidity
environment environment [99].
[99].
Thetypical
The typicalconstructed
constructed devices’
devices’ SEM SEM cross-sectional
cross-sectional images images without
without thecontact
the rear rear contact
are shown in Figure 10a,b. The photos demonstrate the formation
are shown in Figure 10a,b. The photos demonstrate the formation of a thin, homogeneous of a thin, homogeneous
layerof
layer ofspun-on
spun-onc-TiO c-TiO2 2that
thatisis less
less than
than 100
100 nm
nm thick.
thick. When
When compared
compared to to perovskite
perovskite films
created
films withwith
created spin-drop
spin-drop coating,
coating,spray-drop
spray-drop films
filmsare
arethicker
thickerandand less
less homogeneous.
homogeneous. Fig-
ure 10c10c
Figure displays
displays thethecharacteristics
characteristicsofofthe thecurrent
currentdensity
densityand andvoltage.
voltage.The Thearray
arrayofofspray-
spray-drop devices with a 9 mm 2 cell size is seen in the inset image of Figure 10c on a single
drop devices with a 9 mm cell size is seen in the inset image of Figure 10c on a single
2

substrate.
substrate.Additionally,
Additionally, thetheaverage
average PCE from
PCE fromspin-drop
spin-dropcellscells
(8.45%) is greater
(8.45%) than the
is greater than the
average
averagefor forspray-drop
spray-drop cells (5.95%).
cells (5.95%).

Figure10.
Figure 10.SEM
SEM cross-sectional
cross-sectional images
images of planar
of planar PVSCs
PVSCs mademade
by (a) by (a) spin-drop,
spin-drop, (b) spray-drop
(b) spray-drop coating coat-
without a back contact [99]. (c) J-V curves, where the spin-drop and spray-drop coating processes arecoating
ing without a back contact [99]. (c) J-V curves, where the spin-drop and spray-drop
used to create the perovskite layer. The instrument constructed using the spray-drop approach is
seen in the inset [99].
 processes are used to create the perovskite layer. The instrument constructed using the spray-dro
approach is seen in the inset [99].

6. Blade-Coating
Coatings 2022, 12, 1115 13 of 22
The production of each layer of the PSC using scalable coating techniques and th
development of high-performance devices across a vast area are two of the main obstacle
to the effective commercialization of perovskite photovoltaics. The perovskite layer use
6. Blade-Coating
in today’s most effective PSCs is currently made via spin-coating and anti-solvent drip
The production of each layer of the PSC using scalable coating techniques and the
ping to produce dense, pinhole-free layers with good optoelectronic quality [100–103
development of high-performance devices across a vast area are two of the main obstacles
Due
to to the substantial
the effective solution
commercialization of waste generated
perovskite by spin-coating—up
photovoltaics. The perovskite layer to 90%
usedof inthe drip
today’s most effective PSCs is currently made via spin-coating and anti-solvent dripping to process
ping solution might be expelled during spinning [104]—it is not a cost-effective
Additionally,
produce spin-coating
dense, pinhole-free doeswith
layers notgoodproduce films thatquality
optoelectronic are consistent
[100–103].fromDue toonethecorner t
another, which
substantial solution emphasizes
waste generatedlarge-area substrates (>10tocm
by spin-coating—up 90%× 10 cm).dripping
of the In the end, spin-coatin
solution
might
is notbe expelled during
appropriate spinning [104]—it
for continuous R-2-R is not throughput
high a cost-effective process. Additionally,
manufacturing operations an
spin-coating does not produce films that are consistent from one
big area in-line processes. To scale up perovskite photovoltaics, it is desirable corner to another, which to creat
emphasizes large-area substrates (>10 cm × 10 cm). In the end, spin-coating is not appro-
alternative scalable deposition techniques [105].
priate for continuous R-2-R high throughput manufacturing operations and big area in-line
Uniform perovskite films may now be deposited on large-area surfaces using a var
processes. To scale up perovskite photovoltaics, it is desirable to create alternative scalable
ety of industrially
deposition techniquesscalable
[105]. deposition methods that are appropriate for high throughpu
manufacturing.
Uniform perovskiteThesefilmsscalable deposition
may now methods
be deposited may often
on large-area be separated
surfaces into the solu
using a variety
tion-
of and vapor-based
industrially processes.
scalable deposition Blade-coating
methods [106,107],
that are appropriate slot-die-coating
for high throughput man- [108], inkje
printing [109],
ufacturing. Theseand spray-coating
scalable deposition[110]
methods are examples
may often be of separated
solution-based into the techniques
solution- that a
and
lowvapor-based processes.
you to incorporate Blade-coating
additives into the [106,107], slot-die-coating
precursor solution to [108],regulateinkjet print-
film productio
ing [109], and spray-coating
and improve morphology. [110] are examples of solution-based techniques that allow
you to incorporate additives into the precursor solution to regulate film production and
Blade coating offers the benefit of large-area homogeneity, little material waste, in
improve morphology.
terlayer dissolution prevention, compatibility with roll-to-roll manufacturing, and mor
Blade coating offers the benefit of large-area homogeneity, little material waste, in-
efficientdissolution
terlayer use of active materialcompatibility
prevention, while still allowing for the preparation
with roll-to-roll manufacturing, of well-defined
and more film
[111]. The
efficient useblade coating
of active method’s
material while quick-drying
still allowing forstepthe avoids the traditional
preparation solvent annea
of well-defined
ing procedure from slowing down manufacturing throughput
films [111]. The blade coating method’s quick-drying step avoids the traditional solvent [112]. The schematic of th
blade-coating
annealing method
procedure from is presented
slowing downin Figure 11. By
manufacturing altering [112].
throughput the fabrication
The schematic conditions
of the blade-coating
such as the solution method is presented
concentration, theinblade
Figure 11. and
gap, By altering the fabrication
the blade-coating condi-
speed in this pro
tions, such as the solution concentration, the blade gap, and the blade-coating
cess, the film thickness may be adjusted. Using blade-coating techniques, PSC based o speed in this
process, the film thickness may be adjusted. Using blade-coating techniques, PSC based on
PBDTTT-C-T:PCBM was demonstrated, which performed well with the chlorine-free sol
PBDTTT-C-T:PCBM was demonstrated, which performed well with the chlorine-free sol-
vents toluene and xylene [112]. The superior solubility of PBDTTTC-T in the chlorine-fre
vents toluene and xylene [112]. The superior solubility of PBDTTTC-T in the chlorine-free
solvents
solvents is is
thethe primary
primary factor
factor contributing
contributing to the increase
to the increase in PSC performance.
in PSC performance. Additionally, Addition
ally,
the the blade-coated
blade-coated film hadfilm had smoother
smoother surfaces than surfaces than film,
spin-coated spin-coated film, which
which somewhat raisedsomewha
raised
the PCE the PCE
of the of the blade-coated
blade-coated PSC. PSC.

Figure11.11.Blade-coating
Figure Blade-coating setup.
setup.

When P3HT:PCBM PSC was manufactured using several coating processes, including
spin-coating, blade-coating, and blade-coating on a hotplate, in addition to blade and
Coatings 2022, 12, x FOR PEER REVIEW 14 of 23

When P3HT:PCBM PSC was manufactured using several coating processes, includ-
ing spin-coating, blade-coating, and blade-coating on a hotplate, in addition to blade and
Coatings 2022, 12, 1115 14 of 22
spin-coating, the same effect was seen [113]. Because the polymer chains are compara-
tively able to move freely in the absence of centrifugal force, the polymer films produced
by blade-coating with toluene, a chlorine-free solvent, were more structured than those
spin-coating,
produced bythe same effectTherefore,
spin-coating. was seen [113].
it canBecause the polymer
be said that chains areprovide
such approaches comparatively
the nec-
able to move freely in the absence of centrifugal force, the
essary ordered and interpenetrating morphology in polymer films without the polymer films produced byrequire-
blade-
coating with toluene, a chlorine-free solvent, were more structured
ment for any post-production treatment, for instance, solvent annealing and heat anneal- than those produced
by spin-coating. Therefore, it can be said that such approaches provide the necessary
ing.
ordered and interpenetrating morphology in polymer films without the requirement for
One of the main difficulties in producing highly efficient organic-inorganic PSCs is
any post-production treatment, for instance, solvent annealing and heat annealing.
scaling them up [114]. On large-area substrates, uniform perovskite films of good crystal
One of the main difficulties in producing highly efficient organic-inorganic PSCs is
quality have been sought after using a variety of scalable techniques, but each of these
scaling them up [114]. On large-area substrates, uniform perovskite films of good crystal
techniques has its own constraints on the possibility of perovskite photovoltaics’ effective
quality have been sought after using a variety of scalable techniques, but each of these
commercialization. Here, a completely scalable hybrid approach is illustrated that com-
techniques has its own constraints on the possibility of perovskite photovoltaics’ effective
bines vapor- and solution-based
commercialization. Here, a completely methods
scalableto hybrid
produce homogeneous
approach perovskite
is illustrated films of
that combines
excellent quality on surfaces with vast surface areas [115]. This
vapor- and solution-based methods to produce homogeneous perovskite films of excellent two-step procedure avoids
quality on surfaces with vast surface areas [115]. This two-step procedure avoids the useand
the use of hazardous solvents and makes it simple to include passivation techniques of
additives. This technology is used to manufacture PSCs that employ
hazardous solvents and makes it simple to include passivation techniques and additives. blade-coating to de-
posit SnO 2 electron transporting layers and Spiro-OMeTAD hole transporting layers in
This technology is used to manufacture PSCs that employ blade-coating to deposit SnO2
ambienttransporting
electron air without the need
layers forSpiro-OMeTAD
and halogenated solvents. On substrates
hole transporting measuring
layers in ambient5 cmair by
5 cm, the manufactured PSCs attained an open-circuit voltage
without the need for halogenated solvents. On substrates measuring 5 cm by 5 cm, the of up to 1.16 V and a PCE
of 18.7% with good
manufactured PSCs uniformity
attained an[115].
open-circuit voltage of up to 1.16 V and a PCE of 18.7%
The concept
with good uniformity for [115].
the scalable PVD/blade-coating technique to create the perovskite
layerThe
is shown
concept infor
Figure 12a [115].
the scalable The three phases that
PVD/blade-coating make up
technique this hybrid
to create technique.
the perovskite
The inorganic
layer is shown inhalideFiguretemplate
12a [115].isThe
first consecutively
three phases that formed
make upby thisthermal evaporation
hybrid technique. Theon
substrates coated in transparent conducting oxide with an electron
inorganic halide template is first consecutively formed by thermal evaporation on substrates transporting layer
(SnO2).in
coated The layers in this
transparent templateoxide
conducting are 15withnm anthick cesiumtransporting
electron iodide (CsI)layer on the bottom
(SnO of a
2 ). The
300 nminthick
layers lead iodide
this template are(PbI 2) layer.
15 nm thickThe second
cesium stage
iodide involves
(CsI) on theblade-coating
bottom of a 300 the inor-
nm
thick
ganiclead iodide
halide (PbI2 ) layer.
template Theorganic
with the second stage
halideinvolves
precursor blade-coating
solution, whichthe inorganic
is madehalideup of
template with the iodide
formamidinium organic(FAI),
halidemethylammonium
precursor solution, bromide
which is made(MABr), up ofandformamidinium
methylammo-
iodide (FAI), methylammonium
nium chloride (MACl) mixed in bromide (MABr),
isopropanol. Toand methylammonium
encourage chloride (MACl)
crystal development, lessen
mixed in isopropanol. To encourage crystal development, lessen
grain boundaries, and produce a compact perovskite film with a large grain size, thermal grain boundaries, and
produce a compact ◦
annealing at 150 °Cperovskite
for 15 minfilm with a large
in ambient air isgrain size, thermal
performed as theannealing
last step. at SEM150pictures
C for
15
of min in ambient
the film morphologyair is performed
at each stageas the last PVD/blade-coating
of the step. SEM pictures of the film
process morphology
are shown in Fig- at
each stage of
ure 12b–g [115]. the PVD/blade-coating process are shown in Figure 12b–g [115].

Figure 12. Perovskite layers and structure following each phase of the hybrid PVD/blade-coating
technique [115]. (a) A flowchart showing the three stages involved in fabricating a PVD/blade-
coating. Following each phase of manufacturing, SEM top and cross-section view images are shown
in (b,e) after evaporation, (c,f) after blade-coating, and (d,g) after annealing process [115].
Coatings 2022, 12, 1115 15 of 22

7. Other Thin-Film Deposition Methods

Over the past 20 years, a variety of physical and chemical deposition techniques have
been employed to produce nanostructured thin films [116,117]. Both strategies provide
certain advantages over more conventional methods and have a bright future in the de-
position process. New transparent materials must be deposited at low temperatures on
conducting and non-conductive substrates to use thin-film technology.
Physical vapor deposition (PVD) techniques include thermal evaporation [118], elec-
tron beam [119], pulsed laser [120], molecular beam epitaxy [121], ion plating [122], and
activated reactive evaporation [123]. The goal of this deposition technique is to transfer
atoms from a source to a substrate such that independent film formation and growth may
take place. There are several drawbacks, too; for instance, the requirement for a pricey
vacuum environment and expensive instrumentation. The vaporization coating method
known as PVD calls for an atomic-level material transfer. This vacuum-based method
transfers vaporized material from a source to a substrate, where it condenses after passing
through a vacuum or low-pressure gas environment.
The ability to rotate different source materials into the path of the electron, which
prevents the vacuum from being disrupted, is one advantage of E-Beam Evaporation.
E-beam evaporation is widely used for optical thin-film applications, including laser optics,
solar panels, eyeglasses, and architectural glass. A broad variety of materials are deposited
using this method. It provides essential mechanical, electrical, and optical qualities. E-beam
evaporation offers a high material utilization efficiency compared to other PVD processes,
reducing the cost of production.
Chemical vapor deposition (CVD) is a kind of deposition that creates high-performance
solid materials, often in a vacuum. The non-volatile solid thin films that are formed on sub-
strates in this method are created by chemical reactions involving organometallic or halide
chemicals and other gases. The primary distinction between this approach and PVD is the
direction of material deposition on the substrate; PVD is a line-of-site impingement. To
deposit materials in a variety of morphologies, including epitaxial, amorphous, monocrys-
talline, and polycrystalline, CVD is frequently employed in microfabrication techniques.
Contrary to PVD, a solid coating is established on the surface of the substrate because of
a chemical interaction between a mixture of gases and the bulk surface of the material in
CVD. This chemical reaction also allows for the chemical degradation of some of the gas’s
components. Additionally, numerous cutting-edge CVD systems and their alternatives,
such as PECVD [124] and MOCVD [125], have been commercialized. This permits the
assemblies and characteristics of the resultant products to be modified. Typically, CVD does
not need high vacuum working settings, making it a popular technology for electronics,
optoelectronics, and biomedical applications. Numerous papers describe the deposition of
high-quality waveguide films using CVD or its substitutes [126–128].
Research is being performed on a technique called spray pyrolysis for producing thin
and thick films, ceramic coatings, and powders [129]. It stands out as a highly straightfor-
ward and rather cost-effective processing approach, especially when it comes to equipment
expenses, compared to many other film deposition procedures. This technique involves
spraying a solution onto a heated surface, where it reacts to generate a chemical compound,
depositing a thin coating [97]. Chemical reactants are designed so that at the deposition
temperature, products other than the necessary components are volatile. It offers an ex-
ceedingly straightforward method for creating films of any composition. This technique
has been utilized by researchers to create premium thin films that may be used in a variety
of optical components [130–133].
Thin film-based nanomaterials are receiving a lot of interest due to their solid state,
low dimensions, and substantial surface area. Hybrid thin/ultrathin (i.e., with a thickness
of less than 100 nm) films containing different functional components can be used in
cutting-edge research and development, including magnetism, optics, electronics, and
catalysis [134–136]. The direction of current industry developments is toward printable and
flexible photonics and electronics [137]. It has been demonstrated that carbon nanotube
Coatings 2022, 12, 1115 16 of 22

(CNT)-based thin films are strong contenders for these uses [135]. Due to its excellent and
repeatable film quality and production efficiency, vacuum filtering is one of the numerous
production techniques [138,139] that have been widely employed for the fabrication of thin
films [140]. Before being used in actual applications, these thin films must frequently be
deposited onto the necessary substrates. Thin film transfer has thus far proven to be rather
difficult, particularly when applied to diverse substrates and surfaces. Despite being a
helpful approach, the Polydimethylsiloxane (PDMS) stamp transfer method has certain
limitations, such as the inability to transfer onto arbitrary substrates such as curved or holey
surfaces and the inevitable direct contact between the stamp and the film [141]. Another
noteworthy transfer technique has had great success in the manufacturing and transfer of
carbon-based thin films. It is based on solvent-etchable organic membranes, such as mixed
cellulose ester (MCE) filter membranes [142]. The main disadvantage of this approach
is that it can only be used with aqueous dispersion systems, such as CNTs or graphene
suspended in water (H2 O) with the aid of a surfactant.
It is frequently necessary to transfer thin films onto arbitrary substrates or surfaces to
construct thin film-based structures or devices. Although greatly sought, controlling and
non-destructive transfer methods are still difficult to implement. A generic technique for
creating and applying hybrid ultra-thin films. The solution-based in-situ transfer approach
demonstrates both its highly regulated and non-destructive characteristics as well as its
strong capabilities for thin film transfer onto a variety of surfaces. The completely stretched
free-standing thin film is created with a hole structure acting as the support [143]. The
manufacture of thin film-coated complicated optical components is made possible by
the effective transfer to a curved surface. High transparency (>90% in the visible range),
conductivity (1.54 × 104 S/m), and elasticity are displayed in an ultrathin (35 nm) hybrid
film that has been put onto PET (50 µm) (radius of curvature down to mm scale). The
transfer mechanism that has been revealed would offer a strong path to creating intricate
thin film-based structures and systems [143].
In [144], a unique joint manufacturing process was used to create a multilayer barrier
thin film based on polyvinylidene difluoride (PVDF) and SiO2 on a PET substrate. The roll-
to-roll atmospheric atomic layer deposition system (R2R-AALD) was used to deposit the
inorganic SiO2 thin film, and the electrohydrodynamic atomization (EHDA) method was
used to create the organic PVDF layer on the surface of the SiO2 . The surface shape, chemical
composition, and optical characteristics of the multilayer barrier thin films were excellent.
The multilayer barrier thin film’s measured values for arithmetic surface roughness and
water contact angle were 3.88 nm and 125◦ , respectively. The multilayer barrier thin film
had an overall thickness of 520 nm and a high optical transmittance value of 85%–90%. The
barrier thin film’s water vapor transmission rate (WVTR) was 0.9 × 10−2 g·m−2 ·day−1 . For
the creation of multilayer barrier thin films, this dual manufacturing process combination
(R2R-AALD and EHDA) has promise for gas barrier applications [144].

8. Author’s Opinion on Coating Methods and Concluding Remarks

Along with the material to be utilized as a framework for photocatalysts, the coating
technique must be appropriate and well-planned. Given the seriousness, thermal treatments
or methods of acidic solution deposition can destroy the material’s structure. For instance,
unlike glass and metals, polymers cannot resist high temperatures. As a result, the approach
must be appropriate for specific applications. Dip-coating, spray-coating, electrolytic depo-
sition, and thermal attack are the coating methods that have been utilized most often lately.
Other methods, including doctor blades, spin-coatings, and paint-based coatings, have also
been documented, albeit less often. It is also possible to find modifications of these methods,
always attempting to adapt to the coating structure and material type deposition.
In both industrial settings and research labs, spin-coating, dip-coating, and spray-coating
are particularly popular methods for depositing thin films. Due to its great repeatability and
adaptability across a broad viscosity range, spin-coating is one of the vital routes for lab scale.
It is a rapid and simple method to build homogenous films at a tiny scale, ranging in thickness
Coatings 2022, 12, 1115 17 of 22

from a few nanometers to a few micrometers. Due to its high material consumption and
confinement to a broad region, it is not suited for industrial scale-up. Since dip-coating can
easily and quickly deposit thin films over a broad area, it is frequently used for mirror coating
and dye processing. The dip-coating method has the great ability to coat assemblies with
geometries that have concealed faces or tight corners, but there is a significant loss of precursor
solution during the procedure because the container used must hold enough solution to
surround the structure during immersion. The main benefits are the ability to process a big
area and the ability to adjust film thickness by withdrawal speed and solution viscosity. Large
tanks and a lot of coating solutions are needed for dip-coating. Even though the solution has a
lengthy deposition life (a few months), only approximately 20% of it can be utilized.
The spray-coating method allows the flexibility to adjust the system to apply any sort
of solution and achieve the appropriate film thickness. It has access to a wide range of fluids.
It has significant potential for mass manufacturing and is repeatable. The spray-coating
approach can be applied fast if it has the appropriate spray apparatus, but it is not suitable
for irregular geometries with concealed faces. Doctor-blading is a method that works well
for coatings that are applied on a wide scale. The method may also be used to make thicker
films out of a viscous solution. It cannot provide homogeneity at the nanoscale or the very
thin sheets that spin-coating can. In blade-coating, coatings are applied to the paper surface
and then scraped off to smooth the coating’s surface. The knife coater’s steel scraper makes a
difference. The blade coater has the benefit that the coated surface is very flat and unaffected
by the base substrate’s surface quality; high solids coating and high-speed coating are both
achievable, and the coating does not need to be soft and fluid. The coating is typically
not very thick, and it is necessary to maintain the thickness homogeneity of the substrate.
The downside is that when foreign matter is mixed into the coating, it is simple to become
trapped in the edge of the knife, creating lengthy streaks on the surface of the substrate.

Funding: The research is co-financed by the Foundation for Polish Science from the European Regional
Development Fund within the project POIR.04.04.00-00-14D6/18 “Hybrid sensor platforms for inte-
grated photonic systems based on ceramic and polymer materials (HYPHa)” (TEAM-NET program).
Institutional Review Board Statement: Not applicable.
Informed Consent Statement: Not applicable.
Data Availability Statement: Not applicable.
Acknowledgments: The author acknowledge the active contribution of a young researcher Alsu Shak-
maeva in the preparation of high-quality images used in this manuscript.
Conflicts of Interest: The author declares no conflict of interest.

Abbreviations

PVD Physical vapor deposition

CVD Chemical vapor deposition
FHD Flame hydrolysis deposition
ALD Atomic layer deposition
PSCs Perovskite solar cells
PCE Power conversion efficiency
SiO2 :TiO2 Silica-titania
BG Bragg grating
WG Waveguide
NIL Nano-imprint lithography
SEM Scanning electron microscopy
PVA Polyvinyl alcohol
R-2-R Roll-to-Roll
OHAM Optimal homotopy asymptotic method
PDMS Polydimethylsiloxane
PVDF Polyvinylidene difluoride
Coatings 2022, 12, 1115 18 of 22

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