polymers

Review
A Review of Plasma Synthesis Methods for Polymer Films and
Nanoparticles under Atmospheric Pressure Conditions
Hyo Jun Jang 1,† , Eun Young Jung 1,† , Travis Parsons 2 , Heung-Sik Tae 1,3, * and Choon-Sang Park 4, *

1 School of Electronic and Electrical Engineering, College of IT Engineering, Kyungpook National University,
Daegu 41566, Korea; bs00201@knu.ac.kr (H.J.J.); eyjung@knu.ac.kr (E.Y.J.)
2 GBS (Global Business Services) IT, The Procter & Gamble Company, Cincinnati, OH 45202, USA;
trav.parson@gmail.com
3 School of Electronics Engineering, College of IT Engineering, Kyungpook National University,
Daegu 41566, Korea
4 Department of Electronics and Computer Engineering, College of Engineering, Kansas State University,
Manhattan, KS 66506, USA
* Correspondence: hstae@ee.knu.ac.kr (H.-S.T.); purplepcs@ksu.edu (C.-S.P.)
† These authors contributed equally to this work.

Abstract: In this paper, we present an overview of recent approaches in the gas/aerosol-through-

plasma (GATP) and liquid plasma methods for synthesizing polymer films and nanoparticles (NPs)
using an atmospheric-pressure plasma (APP) technique. We hope to aid students and researchers
starting out in the polymerization field by compiling the most commonly utilized simple plasma
synthesis methods, so that they can readily select a method that best suits their needs. Although





 APP methods are widely employed for polymer synthesis, and there are many related papers for
specific applications, reviews that provide comprehensive coverage of the variations of APP methods
Citation: Jang, H.J.; Jung, E.Y.;
Parsons, T.; Tae, H.-S.; Park, C.-S. A
for polymer synthesis are rarely reported. We introduce and compile over 50 recent papers on
Review of Plasma Synthesis Methods various APP polymerization methods that allow us to discuss the existing challenges and future
for Polymer Films and Nanoparticles direction of GATP and solution plasma methods under ambient air conditions for large-area and
under Atmospheric Pressure mass nanoparticle production.
Conditions. Polymers 2021, 13, 2267.
https://doi.org/10.3390/ Keywords: atmospheric-pressure plasma; solution plasma; plasma polymerization; polymer films;
polym13142267 room temperature growth; nanoparticles

Academic Editors: Paola Rizzo and

Antonio Zuorro

1. Introduction
Received: 25 May 2021
Accepted: 6 July 2021
In previous years, many of the papers and studies on polymer synthesis using the
Published: 10 July 2021
atmospheric-pressure plasma (APP) method have focused on specific application processes.
However, there are very few review papers that provide a comprehensive view of the
Publisher’s Note: MDPI stays neutral
polymer synthesis methods using APP, which makes it difficult for new researchers in the
with regard to jurisdictional claims in
field who want to try APP polymer synthesis. Beginning in the 1790s, the report written
published maps and institutional affil- by N. Bondt et al. on polymer synthesis using electrical discharge [1] is seen as one of the
iations. first documented studies on plasma polymerization. In the 19th century, arc synthesis of
hydrocarbons was studied by chemists such as de Wilde et al. [2], Berthelot et al. [3,4], and
P. and A. Thenard [5]. Studies on the synthesis of various organics using glow discharge
were first published by German scientists in the 1960s [6–9]. Afterwards, the first appli-
Copyright: © 2021 by the authors.
cations using these plasma polymers were reported by Goodman [10], and subsequent
Licensee MDPI, Basel, Switzerland.
studies on the property improvements of materials using plasma polymers were actively
This article is an open access article
conducted, with a focus on the interaction between plasma and various substances [11–16].
distributed under the terms and Today, plasma synthesis is selected for various applications, such as layer deposition
conditions of the Creative Commons for electrical devices [17–20], antibio- or bio-material applications [21–24], and surface
Attribution (CC BY) license (https:// modification [25–28], among others.
creativecommons.org/licenses/by/ Plasmas are well known as ionized quasi-neutral gases consisting of photons, neutral
4.0/). particles, metastable particles, ions, radicals, and electrons. Plasmas with the same den-

Polymers 2021, 13, 2267. https://doi.org/10.3390/polym13142267 https://www.mdpi.com/journal/polymers

Polymers 2021, 13, 2267 2 of 28

sity of positive-charged particles (ions) and negative-charged particles (electrons) behave

macroscopically neutrally in free space [29,30]. These plasmas can be artificially generated
by waves, lasers, combustion, flames, and even nuclear reactions, though the most common
approach for plasma generation is electrical discharge from electric power sources in the
laboratory [31,32]. The plasma generated by electric power is called ‘non-equilibrium
plasma’ because the temperature (or kinetic energy) of heavy particles, including ions, is
different from that of the electrons. Only the electrons receive energy from the electric field
generated by applied electric power; thus, the electron temperature (several thousand K) is
relatively higher than the heavy particles’ temperature (around room temperature). This
fact is responsible for the definition of such plasma generated by electric power as ‘cold
plasma’ or ‘non-thermal plasma’ [32]. In the case of polymer synthesis, the non-thermal
plasma method (or non-thermal plasma polymerization) can avoid thermal damage to
substrates or substances due to the relatively low temperatures of the heavy particles. In
addition, the energetic electrons with high energy supplied from plasma can produce high
concentrations of reactive species or free radicals from precursors [32–34]. This method not
only has the degree of freedom for material selectivity without insolubility problems, but
also reduces or eliminates the need for an oxidant or reductant [35–38]. Overall, plasma
polymerization presents several advantages, such as simple installation, high reactivity,
high throughput, fast processing, low cost, low temperature, and green synthesis [39–42].
The non-thermal plasmas are roughly classified into vacuum plasma and APP, de-
pending on the plasma working pressure required—of which APP has substantial potential
for process enlargement because it does not require a high-quality vacuum system, which
significantly reduces the overall setup and operating costs. Such APP can be obtained
under atmospheric pressure conditions, avoiding extreme handling conditions [43]. For
these reasons, polymer synthesis methods using APP have attracted growing attention in
recent years, owing to their high potential for polymer deposition and nanoparticle (NP)
synthesis for various applications [17–28]. Accordingly, attempts to generate plasma under
atmospheric pressure have been successful, and various structures of plasma devices have
been proposed [44–48]. Many reports have described the conditions needed to generate
plasma, and the properties of plasma-synthesized polymers have been thoroughly inves-
tigated [25,39,42,45,49,50]. These studies may lead to further active investigations into
methods and applications of this new plasma equipment in the near future.
We divide these APP polymer synthesis techniques into two types, depending on the
phase of employed precursors: the first is APP polymerization, using a gas- or aerosol-
type precursor [21,39,41], while the second is when the solution itself is supplied as a
precursor [38,43,44], as shown Figure 1. In this review, the former is referred to as the
gas/aerosol-through-plasma (GATP) method, and the latter is denominated as the solution
plasma method. For students and researchers starting out in the APP polymerization
field, the aim of this review is to introduce an overview of recent studies on these polymer
synthesis methods employed by various APP techniques for the formation of polymer
films and NPs. Additionally, the methodological classification of APP polymer synthesis
according to the precursor phase employed, using various kinds of plasma equipment, is
included. The main purpose of this review paper is to provide a reference for recent APP
devices for polymerization, while briefly discussing APP polymerization. We hope that
students and researchers trying to synthesize plasma polymers can then select the best
suited methods for their experiments.
lymers 2021,Polymers
13, x 2021, 13, 2267 3 of 31 3 of 28

(a)

(b)
Figure 1. Representative configuration
Figure 1. Representative of (a) gas/aerosol-through-plasma
configuration (GATP) methods
of (a) gas/aerosol-through-plasma (GATP) (left: jet
methods (left: jet
type, right: dielectric-barrier discharge (DBD) type) and (b) solution plasma methods (left: in-solu-
type, right: dielectric-barrier discharge (DBD) type) and (b) solution plasma methods (left: in-solution
tion plasma, right: on-solution plasma).
plasma, right: on-solution plasma).

2. Synthesis
2. Method Using
Synthesis Gas/Aerosol-Type
Method PrecursorsPrecursors
Using Gas/Aerosol-Type (GATP) (GATP)
GATP methods
GATPuse a discharge
methods use a gas for generating
discharge the APP, and
gas for generating the floated
APP, andprecursors
floated precursors
that are in that
aerosol
are or
in gaseous
aerosol form. Materials
or gaseous form.in aMaterials
gaseous instate at room state
a gaseous temperature
at roomaretemperature
themselvesareapplied as precursors,
themselves appliedwhereas materials
as precursors, that exist
whereas as liquids
materials thatare mainly
exist intro-are mainly
as liquids
duced to a introduced
plasma regionto aas an aerosol
plasma viaasatomizing
region an aerosolorvia
bubbling withorgas.
atomizing GATP meth-
bubbling with gas. GATP
methodsused
ods are commonly are commonly used for
for the deposition ofthe deposition
polymer films of polymer
[51–85], films
as this [51–85],
method as this method
allows
allows in-line
in-line processing by movingprocessing
either by
themoving eitheror
APP devices the APP
the devices[39].
substrates or the substrates [39].

2.1. Atmospheric-Pressure
2.1. Atmospheric-Pressure PlasmaMethod
Plasma Jet (APPJ) Jet (APPJ) Method
An atmospheric-pressure
An atmospheric-pressure plasma jet plasma
(APPJ) isjeta(APPJ)
device is
fora polymerization
device for polymerization
that gen- that gen-
erates directional plasma from a narrow nozzle and a gas flow with high input high
erates directional plasma from a narrow nozzle and a gas flow with input energy.
energy.
Polymerization with APPJ devices enables local processing,
Polymerization with APPJ devices enables local processing, because the process area is because the process area is
limited
limited to the to theplume
jet plasma jet plasma plume size
size [51,59]. [51,59]. Aprecursor
A gas/aerosol gas/aerosol precursor
becomes becomes
activated (or activated
fragmented) by passing through the plasma generation region, and then the fragments fragments
(or fragmented) by passing through the plasma generation region, and then the
become
become neutral neutral
passive (orpassive
recombine)(or recombine)
beyond thebeyond
plasmathe plasma
stream end,stream end,
and are and are deposited
deposited
onto a substrate that lies outside the plasma
onto a substrate that lies outside the plasma region [86,87]. region [86,87].
Zhang et al. [51], Ricci Castro et al. [52], Van Vrekhem et al. [53], and Pandiyaraj et al. [54]
Zhang et al. [51], Ricci Castro et al. [52], Van Vrekhem et al. [53], and Pandiyaraj et
reported an APPJ with pin–ring electrodes. The pin electrode and the ring electrode are
al. [54] reported an APPJ with pin–ring electrodes. The pin electrode and the ring electrode
used as high-voltage (HV) and ground electrodes, respectively. Zhang et al. reported
are used as high-voltage (HV) and ground electrodes, respectively. Zhang et al. reported
an APPJ for poly(methyl methacrylate) (PMMA) coating on a bumpy surface. This APPJ
an APPJ for poly(methyl methacrylate) (PMMA) coating on a bumpy surface. This APPJ
consists of a T-shaped quartz glass body and pin–ring electrodes; the pin electrode is a
consists of a T-shaped quartz glass body and pin–ring electrodes; the pin electrode is a
copper (Cu) rod covered with a quartz glass tube (Figure 2a). Both the plasma discharge
copper (Cu) rod covered with a quartz glass tube (Figure 2a). Both the plasma discharge
Polymers 2021, 13, x
Polymers 2021, 13, 2267 4 of 28

gas and monomer bubbler gas are argon (Ar). In this method, the methyl metha
gas and monomer bubbler gas are argon (Ar). In this method, the methyl methacrylate
(MMA) monomer liquid is housed in a bottle within an oil bath held at 40 °C, and
(MMA) monomer liquid is housed in a bottle within an oil bath held at 40 ◦ C, and is
bled with
bubbled ArArgas
with gas introduced through
introduced through the branch
the branch of thebody
of the quartz quartz
in an body
aerosolin an aeroso
state.
The powergeneration
The power generation usesuses an alternating
an alternating current current (AC)
(AC) source fromsource
10 kHzfrom 10 kHz
to 60 kHz withto 60 kH
a maximum voltage of 17 kV supplied through the pin electrode
a maximum voltage of 17 kV supplied through the pin electrode [51]. [51].

Figure
Figure 2. 2. Structures
Structures of of pin–ring-electrode-type
pin–ring-electrode-type APPJs APPJs
from (a)from
Zhang(a) et Zhang
al. [51], et
(b)al. [51],
Ricci (b) Ricci Ca
Castro
al. [52],
et al. (c)(c)Van
[52], Vrekhem
Van Vrekhem et et
al. al.
[53],[53], andPandiyaraj
and (d) (d) Pandiyaraj etand
et al. [54], al. (e)
[54], and (e)ofschematic
schematic experiment of exper
using aay-shaped
using y-shaped APPJ
APPJwithwith
a ringa powered electrode,
ring powered by Dohertyby
electrode, et Doherty
al. [55]. et al. [55].

Ricci Castro et al. and Van Vrekhem et al. used a similar configuration of the APPJ
Ricci Castro
for synthesizing et al.polymers:
plasma and Van Vrekhem
Two et al.
APPJs were usedthat
utilized a similar
both hadconfiguration
tungsten pin of th
for synthesizing
electrodes; however,plasma
aluminumpolymers:
(Al) and Two
copperAPPJs were
(Cu) were usedutilized that both
as grounded had tungs
ring elec-
trodes. As shown in Figure 2b,c, these APPJ devices consisted of three
electrodes; however, aluminum (Al) and copper (Cu) were used as grounded parts: the head of the rin
trodes. As shown in Figure 2b,c, these APPJ devices consisted of three parts: the h
the device had an HV electrode and a discharge gas inlet; the body was construct
glass tube; and the final component was a plasma nozzle with a grounded ring el
Polymers 2021, 13, 2267 5 of 28

device had an HV electrode and a discharge gas inlet; the body was constructed of a glass
tube; and the final component was a plasma nozzle with a grounded ring electrode and
Polymers 2021, 13, x precursor inlet. In the paper by Ricci Castro et al., Ar was supplied for discharging, and 5 ofan
31
air/acetylene mixture gas was supplied as a precursor. The power source was at 19 kHz
frequency and 17 kVp–p (peak-to-peak) voltage, consisting of two sinusoidal waves with
disparate amplitudes to avoid overheating issues [52]. In the paper by Van Vrekhem et al.,
Vrekhem
Ar gas wasetalso
al., Ar
usedgasaswas also used gas,
the discharge as the discharge
while aerosolgas,
MMA whilewasaerosol
bubbledMMA was
by the Arbub-
gas
bled by the Ar gas and input into the plasma afterglow region; this utilized
and input into the plasma afterglow region; this utilized power generation from a 23-kHz power gener-
ation
AC HVfrom a 23-kHz
source AC HV
to activate thesource
APP [53].to activate the APP [53].
The
The APPJ of Pandiyaraj et al. was fed
APPJ of Pandiyaraj et al. was fed the discharge gas,
the discharge gas, with
with the
the monomer
monomer in in the
the
same path. Both the pin and ring electrodes were made of Cu; the
same path. Both the pin and ring electrodes were made of Cu; the pin Cu electrode was pin Cu electrode was
encapsulated
encapsulated by by aaquartz
quartztube
tube(Figure
(Figure2d).
2d).Triisopropyl
Triisopropyl phosphate
phosphate (TIP)
(TIP) waswas vaporized
vaporized by
by heating to a maximum temperature of up to 500
◦ °C, and the Ar
heating to a maximum temperature of up to 500 C, and the Ar discharge gas carried the discharge gas carried
the TIP
TIP vaporvapor
intointo the inlet.
the inlet. Here, Here,
the ACthe power
AC power (maximum
(maximum voltage
voltage = 40 =kV;
40current
kV; current = 30
= 30 mA;
mA; and frequency = 50 kHz) was supplied to generate
and frequency = 50 kHz) was supplied to generate the APP [54]. the APP [54].
Doherty et etal.al.synthesized
synthesizedthethe plasma
plasma polymer
polymer of heptylamine
of heptylamine onto onto polystyrene.
polystyrene. They
They
used aused a y-shaped
y-shaped quartz quartz capillary
capillary as theasAPPJ
the APPJ
body,body,
with awith a single
single powered
powered ring elec-
ring electrode.
trode.
Helium Helium
gas (He)gasused
(He)for
used for plasma
plasma discharge
discharge was introduced
was introduced in theindownstream
the downstreamflow,flow,
and
and heptylamine
heptylamine aerosolaerosol was bubbled
was bubbled by theby Hethe He introduced
introduced into the into the stream
stream via a branch
via a branch off the
off the quartz
quartz body (Figure
body (Figure 2e). The 2e). The supplied
supplied powerpower
was a was a sinusoidal
sinusoidal currentcurrent
with awith a volt-
voltage of
age of 8 kVp–p
8 kVp–p and a frequency
and a frequency of 10 kHzof 10 kHz [55].
[55].
Kodaira et al. [56], Hossain et al. [57], and Malinowski et al. [58] proposed proposed an APPJAPPJ
with only pin-type electrodes for generating the APP, as shown in Figure 3. Kodaira et et al.
al.
investigated the characterization of APP-polymerized
APP-polymerized hexamethyldisilazane (HMDSN);
they used the same device as the studies from Ricci Castro et al. [52], but without a
grounded ringring electrode
electrode (Figure
(Figure 3a).
3a). The
Thepower
powerwas wasalsoalso
thethe same
same waveform,
waveform, withwith
12
12 kVp–p. Both the discharge gas and HMDSN monomer
kVp–p. Both the discharge gas and HMDSN monomer carrier gas were Ar, carrier gas were Ar, which was
introduced through the upper side and nozzle nozzle of of the
the APPJ,
APPJ, respectively
respectively [56].
[56].

Figure 3.3. Structures of pin

Structures electrode
of pin type in
electrode the in
type APPJs
the of (a) Kodaira
APPJs of (a) et al. [56], et
Kodaira (b)al.
Hossain et al.Hossain
[56], (b) [57], andet(c)al.Malinowski
[57], and
et al. [58].
(c) Malinowski et al. [58].

Hossain etet al.

al. reported
reportedthe
theAPP
APPpolymerization
polymerizationofoftetramethylsilane
tetramethylsilane (TMS) and
(TMS) and3-
aminopropyl(diethoxy)methylsilane
3-aminopropyl(diethoxy)methylsilane(APDMES)
(APDMES)for forsuperhydrophobic
superhydrophobiccoatings
coatings on
on glass.
glass.
The APP
APP was
was generated
generatedfromfromthree
threepin
pinelectrodes,
electrodes,which
which were stainless
were steel
stainless needles
steel ar-
needles
arranged ◦ intervals in a DBD glass reactor. This glass had two branches as a gas
ranged at at 120intervals
120° in a DBD glass reactor. This glass had two branches as a gas in-
inlet—the
let—the upper
upper branchwas
branch wasthe
themain
mainArArgas
gasinlet
inletfor
for discharge,
discharge, while
while the lower branch
guided the precursor flow. A cap was attached to the nozzle component, and nitrogen gas
(N2) was injected to shield the stream from interaction with the ambient air. A mixed liq-
uid of TMS and APDMES was prepared as the precursor, and was bubbled with Ar (Fig-
ure 3b). This plasma reactor was served with AC power at a frequency of 11.5 kHz to
Polymers 2021, 13, 2267 6 of 28

guided the precursor flow. A cap was attached to the nozzle component, and nitrogen gas
(N2 ) was injected to shield the stream from interaction with the ambient air. A mixed liquid
of TMS and APDMES was prepared as the precursor, and was bubbled with Ar (Figure 3b).
Polymers 2021, 13, x 6 of 31
This plasma reactor was served with AC power at a frequency of 11.5 kHz to generate the
APP discharge [57].
A sinusoidal AC HV power source with a peak voltage of 2–6 kV and a frequency
of 20AkHz sinusoidal AC HV power
was applied throughsource
twowithpin aelectrodes
peak voltage
to of 2–6 kV and
generate a frequency
He corona plasma of for
20 kHz was applied through two pin electrodes to generate He corona plasma for the
the deposition of laccase by Malinowski et al. (Figure 3c). The solution of laccase with
deposition of laccase by Malinowski et al. (Figure 3c). The solution of laccase with 10%
10% ethyl alcohol was then atomized by a nebulizer for precursor injection to the plasma
ethyl alcohol was then atomized by a nebulizer for precursor injection to the plasma re-
region [58].
gion [58].
The research groups of Jang et al., Park et al., and Kim et al. [59–62] proposed an APPJ
The research groups of Jang et al., Park et al., and Kim et al. [59–62] proposed an APPJ
with three array jets and a unique shielding system. This system is called the guide-tube
with three array jets and a unique shielding system. This system is called the guide-tube
and bluff-body (GB) system. The guide tube that blocks the plasma reactor from ambient
and bluff-body (GB) system. The guide tube that blocks the plasma reactor from ambient
air isisattached
air attachedtotothethetip
tipofof the
the array
array jets,
jets, andand
thethe bluff
bluff bodybody serves
serves to introduce
to introduce a substrate
a substrate
into the guide tube. The three jets are wrapped with Cu tape as HV electrodes (Figure 4a). 4a).
into the guide tube. The three jets are wrapped with Cu tape as HV electrodes (Figure
Thanksto
Thanks tothe
theambient
ambientairairblocking
blockingandand special
special internal
internal flowflow of GB
of the thesystem,
GB system, it is possible
it is possible
to expand the area of high-density plasma by more than 60 times (Figure 4b) [62]. [62].
to expand the area of high-density plasma by more than 60 times (Figure 4b) They They
synthesized the copolymer [59], pin-hole-free polymer [60], conducting
synthesized the copolymer [59], pin-hole-free polymer [60], conducting polymer [61], and polymer [61], and
single-crystalline polymer [62] using this
single-crystalline polymer [62] using this APPJ device. APPJ device.

Figure
Figure4.4.(a)
(a)Setup
Setup[59] and
[59] (b)(b)
and photo image
photo [62][62]
image of the APPJ
of the withwith
APPJ threethree
arrayarray
jets and
jetsa and
GB system.
a GB system.
(c) Configuration [63] and (d) photo image [64] of the pin-type APPJ with a GB system.
(c) Configuration [63] and (d) photo image [64] of the pin-type APPJ with a GB system.
Kim et al. report a pin-type APPJ with the GB system for synthesizing a conducting
polymer [63] and a transparent polymer [64]. As shown in Figure 4c, this device consists
of four components: a narrow glass for gas inlet, a wide glass tube as the guide tube, a
polytetrafluoroethylene stand as the bluff body, and a tungsten wire electrode to generate
Polymers 2021, 13, 2267 7 of 28

Polymers 2021, 13, x

Kim et al. report a pin-type APPJ with the GB system for synthesizing a conducting 7 of 31
polymer [63] and a transparent polymer [64]. As shown in Figure 4c, this device consists
of four components: a narrow glass for gas inlet, a wide glass tube as the guide tube, a
polytetrafluoroethylene stand as the bluff body, and a tungsten wire electrode to generate
plasma.
plasma. The The tungsten
tungsten wire
wire electrode
electrode is is covered
covered with
with aa glass
glass capillary,
capillary, with
with just
just the
the 2-mm
2-mm
tip
tip of the wire remaining exposed. A discharge gas and a precursor are introduced into
of the wire remaining exposed. A discharge gas and a precursor are introduced into
the
the guide
guide tube
tube via
via the
the gas
gas inlet.
inlet. AA sinusoidal
sinusoidal power
power withwith aa peak
peak voltage
voltage of of 4–5
4–5 kV
kV and
and aa
frequency
frequency of of 30
30 kHz
kHz isis applied
applied through
through the the tungsten
tungsten wirewire electrode,
electrode, forming
formingaa diffused-
diffused-
glow
glow plasma
plasma for
for polymerization
polymerization (Figure
(Figure 4d).
There
There are
are also
also studies
studies using
using commercial
commercial APPJ APPJdevices;
devices;Karl
Karlet etal.
al.[65],
[65],Yan
Yan etet al.
al. [66],
[66],
and
and Yang
Yang et al.
al. [67]
[67] used
used aa commercial
commercial plasma
plasma jetjet instrument
instrument (Plasmatreat
(Plasmatreat AS400 with the
single-nozzle-type
single-nozzle-typePFW10, PFW10,FigureFigure5a)5a) to
to apply
apply aa superhydrophobic
superhydrophobic propertyproperty to to aa target
substrate by polymerizing hexamethyldisiloxane
substrate by polymerizing hexamethyldisiloxane (HMDSO). A frequency of 19 kHz and a
plasma
plasma voltage
voltage ofof 285
285 VV were
were supplied
supplied to to generate
generate the the plasma.
plasma. The The discharge
discharge gas gas (air,
(air, N22,,
oxygen
oxygen (O22)) waswas introduced
introducedinto intothis
this device,
device, while
while the the vapored
vapored precursor
precursor was trans-
was transported
ported to the component
to the nozzle nozzle component by thegas
by the carrier carrier
(Ar, Ngas (Ar,et
2 ). Yan Nal.
2). Yan et al. et
and Yang andal. Yang
put theet plasma
al. put
jet instrument
the plasma jet onto a moving
instrument ontosystem (Figure
a moving 5b), and
system Moosburger-Will
(Figure et al. demonstrated
5b), and Moosburger-Will et al.
that this APPJ that
demonstrated method
this is advantageous
APPJ for in-line processing
method is advantageous [68].processing
for in-line They also[68].usedThey
the same
also
plasma jet (PFW10) for the deposition of methyltrimethoxysilane
used the same plasma jet (PFW10) for the deposition of methyltrimethoxysilane onto 1200 onto 1200 m of carbon
mfiber (Figurefiber
of carbon 5c). Table
(Figure 1 presents
5c). Table a summary
1 presentsof this subsection.
a summary of this subsection.

Figure 5. (a)
(a) The
The plasma jet instrument
instrument schematic
schematic(Plasmatreat
(PlasmatreatAS400
AS400with
withthe
thesingle-nozzle-type
single-nozzle-type PFW10)
PFW10) [65],
[65], and
and setup
setup of
of
(b)(b) polymerization
polymerization of of HMDSO
HMDSO [67]
[67] andand
(c) (c) in-line
in-line processing
processing of carbon
of carbon fiber
fiber [68].
[68].

Table 1. Summary of the synthesis of polymers using APPJ methods.

2.2. Planar Dielectric-Barrier Discharge (DBD) Method
A planar DBD generator is typically a structure in which one or both planar Author
electrodes
No Object Precursor Power Year
are covered by dielectric material in order to avoid arc formation while facing Reference
one an-
other Improvement
[69,70]. When an HV current is applied to one side, a glow plasma is created between
the electrodes. Since the size of the plasma area dependsAron
of flashover the size of the electrodes, it is
gas
Zhang et al.
easier to cover a of
1 performance wider area with this method
methyl-methacrylate (MMA) than with
RFthe APPJ method.
power 2020
[51]
polypropylene (17 kV, 10~60 kHz)
surface
Deposition of Air, Ar gas
polymer film AC Pulse (Sine) Ricci Castro et al.
2 Acetylene 2017
from (12 kV, 19 kHz, 2.8 [52]
Ar/air/acetylene W)
Ar gas
Deposition of Vrekhem et al.
3 MMA AC Pulse power 2018
PMMA film [53]
(23 kHz, 2 W)
Deposition of Ar gas (1 kPa) Pandiyaraj et
4 Triisopropyl phosphate (TIP) 2019
phosphorous AC Pulse power al.
Polymers 2021, 13, 2267 8 of 28

Table 1. Summary of the synthesis of polymers using APPJ methods.

Author
No Object Precursor Power Year
Reference
Improvement of flashover Ar gas
Zhang et al.
1 performance of methyl-methacrylate (MMA) RF power 2020
[51]
polypropylene surface (17 kV, 10~60 kHz)
Air, Ar gas
Deposition of polymer film Ricci Castro et al.
2 Acetylene AC Pulse (Sine) 2017
from Ar/air/acetylene [52]
(12 kV, 19 kHz, 2.8 W)
Ar gas
Vrekhem et al.
3 Deposition of PMMA film MMA AC Pulse power 2018
[53]
(23 kHz, 2 W)
Deposition of phosphorous Ar gas (1 kPa)
Pandiyaraj et al.
4 containing Triisopropyl phosphate (TIP) AC Pulse power 2019
[54]
functional coatings (40 kV, 50 kHz)
He gas
Polymerization Doherty et al.
5 Heptylamine AC Pulse (Sine) 2019
of heptylamine [55]
(8 kV, 10 kHz)
Air, Ar gas
Kodaira et al.
6 Polymerization of HMDSN Hexamethyldisilazane (HMDSN) AC Pulse (Sine) 2017
[56]
(12 kV, 19 kHz, 2.8 W)
Tetramethylsilane (TMS),
Ar gas
3- Hossain et al.
7 Superhydrophobic coating RF power 2019
aminopropyl(diethoxy)methylsilane [57]
(7.5 kV, 11.5 kHz)
(APDMES)
He gas
Malinowski et al.
8 Durable bioactive coating Laccase AC Pulse 2018
[58]
(2∼6 kV, 20 kHz)
Ar gas
Jang et al.
9 Copolymerization Mixture of thiophene and Aniline AC Pulse (Sine) 2020
[59]
(23 kV, 26 kHz)
Ar gas
Park et al.
10 Polymerization of PMMA MMA AC Pulse (Sine) 2019
[60]
(12 kV, 30 kHz)
Ar gas
Humidity-independent Park et al.
11 aniline AC Pulse (Sine) 2017
conducting polymer [61]
(8 kV, 26 kHz)
Ar gas
Single-crystalline Kim et al.
12 Pyrrole AC Pulse (Sine)(12 kV, 2017
polymer film [62]
30 kHz)
Ar gas
Kim et al.
13 Conducting polymer film aniline AC Pulse (Sine) 2021
[63]
(5 kV, 30 kHz)
Ar gas
Kim et al.
14 Transparent thin film aniline AC Pulse (Sine) 2021
[64]
(4 kV, 30 kHz)
Air, N2 gas
Deposition from HMDSO, Tetraethyl orthosilicate Karl et al.
15 Pulse power 2020
organosilicon (TEOS) [65]
(19 kHz, 1 kW)
Preservation of Air, Ar gas Yan et al.
16 HMDSO 2019
paper-based relics Pulse power [66]
O2 , N2 gas
Superhydrophobic Yang et al.
17 HMDSO RF power 2018
cotton fabrics [67]
(19 kHz)
Ar gas
Reinforcement of Moosburger-Will et al.
18 Methyltrimethoxysilane (MTMS) AC Pulse 2017
carbon fiber [68]
(252 V, 21 kHz, 600 W)

Pandivaraj et al. [69], Ramkumar et al. [70], Mertens et al. [71], Getnet et al. [72],
and Dvorˇáková et al. [73] report polymer deposition by using planar DBD with fixed
electrodes, as shown in Figure 6. Pandivaraj et al. used a plasma generator with a typical
DBD structure to increase the antifouling properties of low-density polyethylene (LDPE)
films by copolymerizing. This plasma generator consisted of two square electrodes covered
by a dielectric material sheet (polypropylene with a thickness of 3 mm) and a chamber.
Two electrodes were placed in the chamber with a separation distance of 7 mm. The
LDPE film was placed on the lower electrode (grounded electrode), and the plasma was
generated by AC power with a voltage of 40 kV and a frequency of 50 Hz through the
Polymers 2021, 13, 2267 9 of 28

upper electrode (powered electrode) (Figure 6a). Thereafter, a mixture vapor of acrylic
acid and polyethylene glycol (PEG) produced by heat (80 ◦ C and 220 ◦ C respectively)
was fed into the chamber [69]. Ramkumar et al. used the same device and procedure as
Pandivaraj et al.; however, they employed PEG methyl ether methacrylate (PEGMA) as a
precursor to enhance the biocompatibility of LDPE films. The gap between the electrodes
was 5 mm and the PEGMA vapor was prepared at 60 ◦ C [70].
Mertens et al. employed two electrodes covered with different dielectric materials for
hydrophilic and hydrophobic coatings for about 11 substances. The upper Cu electrode
(powered electrode) and the lower Cu electrode (grounded electrode) were covered by a
3-mm-thick α-alumina and a 2-mm-thick borosilicate, respectively. The gap between the
two electrodes was 4 mm. This plasma generation system was placed in a Pyrex glass
cylinder chamber. The inside of the chamber was pumped down to 270 Pa and filled to
atmospheric pressure with Ar. The precursor bubbled by a secondary flow was introduced
into the plasma region by diluting it with the primary flow (Figure 6b) [71].
Getnet et al. conducted the deposition of carvacrol thin film on a stainless steel
substrate using a DBD generator with only the lower-side electrode (grounded electrode)
covered with a polyester sheet as a dielectric layer. Two parallel circular brass electrodes
were fixed at 3 mm. A sinusoidal AC pulse with a frequency of 60 Hz and a maximum
voltage of 15 kV was applied to the upper electrode (powered electrode). Ar at a flow of
5 L/min was used for the plasma discharge and vaporizing the carvacrol (Figure 6c) [72].
Dvorˇáková et al. used diffuse coplanar surface barrier discharge (DCSBD) methods
for fast surface hydrophilization. The DCSBD device was described as a set of parallel,
strip-like molybdenum electrodes embedded in alumina as a dielectric material [88]. The
thin-layer plasma was generated on the DCSBD surfaces when a high-voltage sine wave
was applied to DCSBD electrodes. The substrate holder was fixed at 0.1 mm from the
DCSBD surface. A gas mixture of propane, butane, and N2 was supplied via a gas inlet in
the middle of the substrate holder (Figure 6d) [73].
Bardon et al. [74], Manakhov et al. [75], Obrusník et al. [76], and St’ahel et al. [77] used
a movable upper electrode with a gas inlet for improving the deposition uniformity [75],
as shown in Figure 7. Bardon et al. improved the coating’s mechanical properties by using
DBD plasma and mixtures of dodecyl acrylate (DOCA) with 1,6-hexanediol diacrylate
(HdiA) or 1,6-hexanediol dimethacrylate (HdiMA) as precursors. The DBD generator
consisted of an earthed-bottom aluminum plate and two powered aluminum top plates
covered with a 3.25 mm-thick glass plate. The gap between the bottom electrode and the
glass plate was set to 2 mm. The bottom electrode had a slot as a sample holder to set the
surface of the samples and the electrode at the same level (Figure 7a) [89]. The precursor
mixture was atomized to an aerosol state using He, entering the space between the top
electrodes. For the plasma generation, an AC power of 110 W with a peak-to-peak voltage
of 11 kV was used [74].
Manakhov et al. utilized a DBD plasma system to copolymerize maleic anhydride
(MA) and C2 H2 for carboxyl-rich coatings in a metallic cube chamber. The two rectangular
pieces were separated to provide room for the gas feed, while the top electrode was covered
with Al2 O3 ceramics with a thickness of 1 mm, and the bottom metallic electrode (grounded
electrode) was also covered with the ceramic. The gap between the top and bottom ceramics
was set at 1.6 mm (Figure 7b). This chamber was pumped down, and then filled up to
96 kPa with Ar, MA, and C2 H2 as a deposition gas mixture. The plasma was ignited by a
sinusoidal wave with a frequency of 5–6.6 kHz and a power of 8 W [75]. Obrusník et al.
and St’ahel et al. used a plasma-generating system with the same electrode configuration as
Manakhov et al., albeit in open air; the gas was supplied through the inlet in the middle of
the top electrode connected to a 4-cm-long rectangular duct (Figure 7c) [76]. In the work of
St’ahel et al., a heating spiral was added to the bottom electrode along with a thermocouple
to increase the substrate temperature, and the gap between the electrodes was changed to
1.0 mm (Figure 7d) [77].
Polymers 2021,13,
Polymers2021, 13,2267
x 10
10of
of28
31

Figure 6.
Figure 6. The
The polymerization
polymerization systems
systemsusing
usingplanar
planarDBD
DBDofof(a)
(a)Pandivaraj
Pandivarajetet
al.al.
[69], (b)(b)
[69], Mertens et
Mertens
al. [71], (c) Getnet et al. [72], and (d) Dvorˇáková et al. [73].
et al. [71], (c) Getnet et al. [72], and (d) Dvorˇáková et al. [73].

Bardon etetal.al.[74],
Demaude [78],Manakhov
Nisol et al.et[79],
al. [75], Obrusník
Jalaber et Ma
et al. [80], al. [76],
et al.and
[81],St’ahel
Ondo et et al.
al.[82],
[77]
used a movable upper electrode with a gas inlet for improving the
and Loyer et al. [83–85] employed a DBD plasma generator with a moving substrate stagedeposition uniformity
[75], as shown
(bottom in Figure
electrode) 7. Bardon et coverage
for homogeneous al. improvedand the coating’s
scale-up mechanical
[79,81], as shown properties
in Figureby 8.
using DBDetplasma
Demaude al. and and mixtures
Nisol et al. of dodecyl acrylate
synthesized (DOCA)
a polymer with 1,6-hexanediol diacry-
for hydrophilic/phobic patter
late (HdiA)
coating [78] or 1,6-hexanediol
and age-resistantdimethacrylate (HdiMA) as precursors.
coating [79], respectively. In this DBDThe DBD device,
plasma generator a
consisted
long of an earthed-bottom
aluminum strip covered with aluminum plate and
a 4-mm-thick two powered
borosilicate glass aluminum top plates
plate was used as a
covered with
movable lowera 3.25 mm-thick
electrode, glass
while theplate.
upper The gap between
electrode the bottom
consisted of twoelectrode
Cu plates, and the
with
glass plate was set to 2 mm. The bottom electrode had a slot as a sample
a separation between the plates for a gas/precursor inlet. Both the discharge gas and holder to set the
surface ofbubbling/carrier
precursor the samples and gas the were
electrode at the same
Ar (Figure level (Figure 7a) [89]. The precursor
8a) [78,79].
mixture was atomized to an aerosol state using He, entering the space between the top
electrodes. For the plasma generation, an AC power of 110 W with a peak-to-peak voltage
of 11 kV was used [74].
Polymers 2021, 13, 2267 11 of 28
Polymers 2021, 13, x 11 of 31

Figure 7. The polymerization systems using planar DBD with a movable top electrode (powered electrode) of (a) Bardon
Figure
Polymers 13,The
2021,7. x polymerization systems using planar DBD with a movable top electrode (powered electrode) of (a) Bardon
12 of 31
et al. [74,89], (b) Manakhov et al. [75], and (c) Obrusník et al. [76], and the image of the DBD system of (d) St’ahel et al.
et al. [74,89], (b) Manakhov et al. [75], and (c) Obrusník et al. [76], and the image of the DBD system of (d) St’ahel et al. [77].
[77].

Manakhov et al. utilized a DBD plasma system to copolymerize maleic anhydride

(MA) and C2H2 for carboxyl-rich coatings in a metallic cube chamber. The two rectangular
pieces were separated to provide room for the gas feed, while the top electrode was cov-
ered with Al2O3 ceramics with a thickness of 1 mm, and the bottom metallic electrode
(grounded electrode) was also covered with the ceramic. The gap between the top and
bottom ceramics was set at 1.6 mm (Figure 7b). This chamber was pumped down, and
then filled up to 96 kPa with Ar, MA, and C2H2 as a deposition gas mixture. The plasma
was ignited by a sinusoidal wave with a frequency of 5–6.6 kHz and a power of 8 W [75].
Obrusník et al. and St’ahel et al. used a plasma-generating system with the same electrode
configuration as Manakhov et al., albeit in open air; the gas was supplied through the inlet
in the middle of the top electrode connected to a 4-cm-long rectangular duct (Figure 7c)
[76]. In the work of St’ahel et al., a heating spiral was added to the bottom electrode along
with a thermocouple to increase the substrate temperature, and the gap between the elec-
trodes was changed to 1.0 mm (Figure 7d) [77].
Demaude et al. [78], Nisol et al. [79], Jalaber et al. [80], Ma et al. [81], Ondo et al. [82],
and Loyer et al. [83–85] employed a DBD plasma generator with a moving substrate stage
(bottom electrode) for homogeneous coverage and scale-up [79,81], as shown in Figure 8.
Demaude et al. and Nisol et al. synthesized a polymer for hydrophilic/phobic patter coat-
Figure 8.8.TheThepolymerization
polymerization systems
ing [78] usingage-resistant
and
systems planarplanar
using DBD with a movable
coating
DBD with[79],a substrate stage
respectively.
movable (bottom
In this
substrate electrode)
DBD
stage of electrode)
plasma
(bottom (a)device,
Demaude a long
of
et al.
(a) [78], (b) et
Demaude Jalaber et al.
al. [78], (b)[80], (c) Ma
aluminum
Jalaber et al.etstrip
al. [81],
[80], (c) andet(d)
covered
Ma Loyer
with
al. et al.
[81],aand (d)[83].
4-mm-thickLoyer borosilicate
et al. [83]. glass plate was used as a movable
lower electrode, while the upper electrode consisted of two Cu plates, with a separation
Jalaber
between theet
Jalaber et al.
al.used
plates forDBD
used a DBD plasma
plasma
gas/precursor polymerization
polymerization
inlet. Both the for discharge
eco-friendly
for gasand
eco-friendly and catalyst-free
and pol-
catalyst-free
precursor bub-
ymer
polymersynthesis.
synthesis. Their device
Their device ignited
bling/carrier gas were Ar (Figure 8a) [78,79]. ignited the
theDBD
DBD plasma
plasma from
from between
between two
two plane-parallel
HV electrodes covered
HV electrodes coveredwith withalumina
aluminaand and a movable
a movable substrate
substrate stage
stage as aas a grounded
grounded elec-
electrode.
The distance
trode. The distancebetween the HV
between theelectrodes
HV electrodesand the and substrate stage stage
the substrate was 1was mm.1 mm.
A 10 A kHz10
sinusoidal
kHz sinusoidal voltage
voltagewaswas applied
appliedthrough
through two twoplane-parallel
plane-parallelelectrodes
electrodesto togenerate
generate the
plasma. Dopamine
plasma. Dopamine acrylamideacrylamide as as the
the precursor
precursor was was atomized
atomized using
using aa nebulizer, and its
flow was controlled with a syringe pump (Figure 8b) [80].
flow
Ma et
Ma etal.al.utilized
utilizeda aplasma
plasma device
device with
with a rolling
a rolling electrode
electrode system;
system; twotwo cylindrical
cylindrical HV
HV electrodes
electrodes (Ф = (Φ = 4 mm;
4 mm; length length
= 100=mm) 100 mm)werewere
fixedfixed
at a at a distance
distance of 7 ofmm 7 mm
fromfrom the
the top
top layer
layer and and the bottom
the bottom layerlayer
of the ofoutlet
the outlet
of theofgas
thechamber.
gas chamber. The cylindrical
The cylindrical groundground
elec-
electrode
trode (Ф = (Φ = 60 mm;
60 mm; length length
= 100 = 100was
mm) mm)made was made of stainless
of stainless steel
steel and and controlled
controlled by a
by a motor.
motor. Within the triple-inlet gas chamber, some glass wool pieces
Within the triple-inlet gas chamber, some glass wool pieces were placed inside to provide were placed inside to
provide gas flow homogeneity. The ground electrode was
gas flow homogeneity. The ground electrode was wrapped in the PET substrate (Figure wrapped in the PET substrate
8c). A 13.56 MHz RF power source with 30 W applied through the HV electrodes ignited
the plasma in open-air conditions [81].
Ondo et al. and Loyer et al. used a polymerization method called plasma-initiated
chemical vapor deposition (PiCVD). This method is characterized by the usage of an ultra-
Polymers 2021, 13, 2267 12 of 28

(Figure 8c). A 13.56 MHz RF power source with 30 W applied through the HV electrodes
ignited the plasma in open-air conditions [81].
Ondo et al. and Loyer et al. used a polymerization method called plasma-initiated
chemical vapor deposition (PiCVD). This method is characterized by the usage of an
ultra-short square-wave pulse power to ignite the DBD plasma for the deposition of
a polymer film with a high degree of polymerization [82–85]. This plasma generator
consisted of two parallel HV electrodes made of alumina and a movable stage as the
ground electrode [90]. The gap between the parallel electrodes and the ground electrode
was maintained at 1 mm (Figure 8d). An ultra-short square-wave pulse was employed to
generate the plasma with an extremely low plasma duty cycle (ton /(ton + toff )); a very low
duty cycle plasma (0.1~0.001%) was employed for their studies [82–85]. Table 2 shows a
summary of this subsection.

Table 2. Summary of the synthesis of polymer films using planar DBD plasma.

Author
No Object Precursor Plasma Source Year
Reference
Ar gas
Improvement of mixture of acrylic acid (AAC) and Pandiyaraj et al.
1 AC Pulse 2019
antifouling properties poly (ethylene glycol) (PEG) [69]
(14 kV, 44 kHz)
Ar gas
poly (ethylene glycol) methylether Ramkumar et al.
2 Enhancement of biocompatibility AC Pulse 2017
methacrylate (PEGMA) [70]
(14 kV, 44 kHz)
Ar gas
Hydrophilic and 11 precursors for hydrophilic and Mertens et al.
3 AC Pulse 2020
hydrophobic coatings hydrophobic coatings [71]
(17.1 kHz)
Carvacrol Ar gas
Inhibition of bacteria adhesion and Getnet et al.
4 (5-Isopropyl-2-methylphenol, AC Pulse 2020
proliferation [72]
(CH3 )2 CHC6 H3 (CH3 )OH) (15 kV, 60 Hz)
N2 gas
Dvorˇáková et al.
5 Surface hydrophilization propane-butane (PB) gas AC Pulse 2019
[73]
(30 kHz)
Dodecyl acrylate (DOCA),
He gas
Reinforcement of mechanical 1,6-hexanediol diacrylate (HdiA), Bardon et al.
6 AC Pulse 2018
properties of DOCA film 1,6-hexanediol dimethacrylate [74]
(11 kV, 10 kHz, 110 W)
(HdiMA)
Ar gas
Manakhov et al.
7 Carboxyl-rich coatings maleic anhydride (MA), acetylene AC Pulse (Sine) 2016
[75]
(4 kV, 5∼6.6 kHz, 8 W)
Ar gas
Obrusník et al.
8 Copolymerization MA, acetylene AC Pulse 2017
[76]
(4 kV, 4 kHz, 3.3 W)
Ar gas
Antibacterial properties and 2-methyl-2-oxzoline, polyoxazoline St’ahel et al.
9 AC Pulse 2019
cytocompatibility performance (POx) [77]
(6 kHz, 55 W)
Ar, O2 gas
acrylic acid (AA) Demaude et al.
10 Hydrophilic/phobic patterns AC Pulse (Sine) 2019
propargyl methacrylate (PMA) [78]
(16.2 kHz, 90 W)
Ar gas
Age-resistant coatings with tunable Nisol et al.
11 AA, PMA AC Pulse (Sine) 2016
wettability [79]
(15.64 kHz, 30 to 90 W)
dopamine acrylamide (DOA) Ar, O2 gas
Preparation of tunable Jalaber et al.
12 2-hydroxyethyl AC Pulse (Sine) 2019
catechol-bearing thin films [80]
methacrylate monomer (HEMA) (10 kHz)
Ar gas
Ma et al.
13 Hydrophilicity HMDSO 13.56 MHz RF 2020
[81]
(30 W)
N2 gas
Ondo et al.
14 Low-k Polymer Insulating Layers 4 cyclic organosilicon monomers AC square Pulse 2019
[82]
(6 kV, 100 Hz)
Comparison of polymer properties 3 methacrylate monomers Ar gasAC square Pulse Loyer et al.
15 2017
according to applied duty cycle (MMA, BMA, GMA) (6.5 kV, 10 kHz) [83]
Polymers 2021, 13, 2267 13 of 28

Table 2. Cont.

Author
No Object Precursor Plasma Source Year
Reference
Ar gas
Comparison of polymer properties 2 methacrylate monomers Loyer et al.
16 AC square Pulse 2018
according to applied duty cycle (MMA, GMA) [84]
(6.5 kV, 10 kHz)
Deposition of NVCL with N-vinyl caprolactam (NVCL) Ar gas
Loyer et al.
17 water-stable and ethylene glycol dimethacrylate AC square Pulse 2019
[85]
thermo-responsive properties (EGDMA) (6.5 kV, 10 kHz)

3. Synthesis Method Using Liquid-Type Precursors

APP synthesis methods using liquid-type precursors leverage the interaction between
APP and a bulk liquid precursor. The complicated chemical and physical reactions at the
plasma–liquid interface cause reduction, oxidation, and sputtering. In most cases, NPs are
synthesized from the various radicals generated by the plasma–liquid reactions [43,91].
This method is classified into two types, depending on the location of the APP generation.

3.1. Atmospheric-Pressure Plasma (APP) Generated by Outside Bulk Liquid Precursors

APP generated on the outside of bulk liquid precursors—so-called (on-solution
plasma)—is affected by natural air components. Therefore, chemical and physical reactions
at the plasma–liquid interface take place with various species caused by the interaction
between the APP and air components such as O3 , N2 O5 , N2 O, NHO3 , H2 , NO3 , H2 O2 ,
HNO2 , and NO2 [38]. Complex reactions that are not well understood due to various
radicals can produce unusual results [92].
Tan et al. [93,94], Schäfer [95] et al., Zhang et al. [96], and Gamaleev et al. [97] used on-
solution plasma generated by various methods, as shown in Figure 9. Tan et al. employed
an APPJ with a cross-shaped borosilicate glass body with five nozzles as a plasma outlet,
two inlets for Ar flow as a discharge gas, and two side tubes for the electrodes. The power
and ground electrodes were made of tungsten, with a separation of 5 mm (Figure 9a). An
AC power source with a voltage of 15 kV and a frequency of 60 Hz was applied from a
neon sign transformer to ignite the APP. This APP treats the surface of styrene [93] and
MMA [94] as bulk liquid precursors (Figure 9b).
Schäfer et al. synthesized three liquid organosilicon compounds (HMDSO, octamethyl-
tetrasiloxane, and tetrakis(trimethylsilyloxy)silane) as precursors using a commercial APPJ
(kINPen 11; neoplas tools, Greifswald, Germany). This commercial APPJ consisted of a
powered pin electrode centered in a ceramic capillary and a grounded outer ring electrode.
Ar gas was introduced as a discharge gas through the ceramic capillary (Figure 9c). A
power source of 5 W with a frequency of 1.1 MHz was needed to generate the APP. Liquid
precursors were applied to the surface of the substrate, and these were synthesized by
exposure to the APP (Figure 9d) [95].
Zhang et al. utilized the discharge between a stainless steel capillary and a liquid bulk
surface to synthesize the metallic NPs embedded in a conducting polymer. In this research,
the liquid precursor was HAuCl4 aqueous solution added to poly(3,4-ethylenedioxy thio-
phene) polystyrene sulfonate (PEDOT:PSS). This APP generator system used a stainless
steel capillary as the powered electrode and a carbon rod as the grounded electrode. The
stainless steel capillary also acted on the APPJ generating the He plasma. The distance be-
tween the tip of the capillary and the surface of the liquid precursor was 0.9 mm (Figure 9e).
The APP was ignited by direct current (DC) with a voltage of 2 kV, and maintained by a
voltage of 0.8 kV [96].
Gamaleev et al. employed a pin-type electrode for the generation of on-solution
plasma to produce nanographene. First, 100 mL of ethanol liquid precursor was placed
in a beaker. A Cu plate grounded electrode was immersed in the ethanol, and a Cu rod
powered electrode was placed in the air. The beaker was filled in at a flow rate of 5 slm
(Figure 9f) [97]. Table 3 contains a summary of this subsection.
 Polymers 2021, 13, 2267 14 of 28
Polymers 2021, 13, x 15 of 31

Figure
Figure9.9.Schematics
Schematicsofofgeneration
generationofofthe
theon-solution
on-solutionplasma
plasmasystems
systemsofof(a, b) Tan
(a,b) Tan et
et al.
al. [93,94],
[93,94], (c,
(c,d)
d)Schäfer
Schäfer[95]
[95]etetal.,
al.,(e)(e)Zhang
Zhang et al. [96], and (f) Gamaleev et al. [97].
et al. [96], and (f) Gamaleev et al. [97].

TableSchäfer et al.ofsynthesized
3. Summary syntheses using three liquid organosilicon
on-solution plasma methods. compounds (HMDSO, octame-
thyltetrasiloxane, and tetrakis(trimethylsilyloxy)silane) as precursors using a commercial
Author
No ObjectAPPJ (kINPen 11; neoplas Precursortools, Greifswald, PlasmaGermany).
Source This commercial
Year APPJ consisted
Reference
of a powered pin electrode centered in a ceramic Ar gas
capillary and a grounded outer ring
Tan et al.
1 Plasma-treatedelectrode.
styrene Ar gas wasStyrene introduced as a discharge gas through the
AC Pulse ceramic capillary
2018
[93]
(Figure
(15 kV, 60 Hz, 450 W)
9c). A power source of 5 W with a frequency of 1.1 MHz was needed to generate the APP.
Ar gas
2 Plasma-treatedLiquid
MMA precursors were applied to the surface
MMA ACof the substrate, and
Pulse 2020 these were synthesized
Tan et al.
[94]
by exposure to the APP (Figure 9d) [95]. (15 kV, 60 Hz, 450 W)

Zhang et al. utilized HMDSO,the discharge between a stainless steel capillary and a liquid
octamethyltetrasiloxane Ar gas
bulk Schäfer et In
al. this
3 Thin, solid SiO x filmsurface to synthesize (OMCTS),the metallic NPsAC embedded
Pulse in a conducting
2017 polymer.
[95]
tetrakis(trimethylsilyloxy)silane (1.1 MHz, 5 W)
research, the liquid precursor (TTMS)
was HAuCl4 aqueous solution added to poly(3,4-ethylene-
dioxy thiophene) polystyrene sulfonate
HAuCl4 aqueous solution,
(PEDOT:PSS).
He gas
This APP generator system used a
4 stainless steel capillary as the powered electrode and a carbon2017
Metallic NPs embedded in a poly(3,4-ethylenedioxy DC Pulse rod as the grounded
Zhang et al. elec-
conducting polymer thiophene) polystyrene sulfonate (ignition 2 kV, maintain [96]
trode. The stainless(PEDOT:PSS)steel capillary also acted0.8 onkV)the APPJ generating the He plasma. The
distance between the tip of the capillary and the surface of the liquid precursor Gamaleevwaset al. 0.9
5 Nanographene Ethanol AC high voltage 2018
mm (Figure 9e). The APP was ignited by direct current (DC) with a voltage of[97] 2 kV, and
maintained by a voltage of 0.8 kV [96].
3.2. Gamaleev et al. employed
Atmospheric-Pressure Plasma (APP)a pin-type
Generatedelectrode for Bulk
by Inside the generation of on-solution
Liquid Precursors
plasma to produce nanographene. First, 100 mL of ethanol
In this section, in-solution plasma is defined as generating the APP in liquidliquid precursor wasprecursors.
placed in
aIn-solution
beaker. A Cu plasma is mostly generated between tungsten pin-to-pin electrodes. One pow-
plate grounded electrode was immersed in the ethanol, and a Cu rod of the
ered electrode was placed
structurally critical pointsinofthetheair. The beaker
in-solution was filled
plasma system in at a flow
is the gaprate of 5 slm
between (Figure
electrodes;
9f)
the[97].
gapTable 3 contains
can induce a summary
a breakdown of this subsection.
of plasma in liquid media [98–100]; therefore, tungsten is
commonly chosen for synthesis using an in-solution plasma due to its high melting point,
Polymers 2021, 13, 2267 15 of 28

corrosion resistance, high stability, and good electrical conductivity [101,102]. Since the
in-solution plasma is immersed in the solution, only reactions between the plasma and
the solution occur in their entirety. Many recent papers about synthesis methods using
in-solution plasma have mostly been reported on the formation of NPs [103–112].
Hyun et al. [103,104], Panomsuwan et al. [105], Morishita et al. [106], Lee et al. [107],
Li et al. [108], Tipplook et al. [109], and Lee et al. [91] used in-solution plasma systems
generated by the plasma discharge between tungsten pin-to-pin electrodes, and Alsaeedi
et al. [110] chose carbon rods as the electrodes, as shown in Figures 10–12. Hyun et al. used
a pair of tungsten electrodes 1 mm in diameter to generate the in-solution plasma; these
electrodes were located at a distance of 1.5 mm from the glass reactor. A bipolar HV pulse
of 2 kV with a repetition frequency of 25–200 kHz and a pulse width of 1 µs was applied
via the electrodes. Liquid precursors such as N-methyl-2-pyrrolidone, 2-pyrrolidone,
Polymers 2021, 13, x pyrrolidine, 1-methylpyrrolidine, pyrrole, cyclopentanone, and cyclohexanone were17used of 31
for the synthesis of nitrogen–carbon nanosheets (Figure 10a) [103,104].

Figure
Figure10.10.Representative figures
Representative on the
figures ongeneration of the in-solution
the generation plasma systems
of the in-solution plasmaofsystems
(a) Hyunof
et
(a)al.Hyun
[104],et(b)
al.Panomsuwan et al. [105],etand
[104], (b) Panomsuwan (c) Morishita
al. [105], et al. [106].et al. [106].
and (c) Morishita

Panomsuwan et al. also used a pair of tungsten electrodes 1 mm in diameter. The

electrodes were covered with an insulating ceramic tube, and had a gap of 1 mm. The
bipolar power source used had a pulse duration of 0.80 µs and a frequency of 20 kHz.
In-solution plasma was initiated and stably maintained inside 100 mL of liquid precur-
sor under vigorous stirring (Figure 10b). Cyano-aromatic molecules (2-cyanopyridine,
cyanopyrazine) were used as liquid precursors for the synthesis of nitrogen-doped carbon
NPs (NCNPs) [105].
Morishita et al. also employed tungsten electrodes 1 mm in diameter for in-solution
plasma. The electrodes were covered with a ceramic segment, and the distance between
them was set to 0.5 mm. The applied voltage was about 1.7 kV, the repetition frequency
was 15 kHz, and the pulse width was 1.0 µs. The precursors for the fast formation of
nanocarbons were hexane, hexadecane, cyclohexane, and benzene. For the extraction of
nanocarbons, plasma-treated precursors were dried at 100 °C in an oven (Figure 10c) [106].
 Polymers 2021, 13, 2267 16 of 28
Figure 10. Representative figures on the generation of the in-solution plasma systems of (a) Hyun
et al. [104], (b) Panomsuwan et al. [105], and (c) Morishita et al. [106].

ers 2021, 13, x Figure

Figure 11.
11. Schematics
Schematicsofofgeneration
generationofof
the in-solution
the plasma
in-solution systems
plasma of of
systems (a) (a)
LeeLee
et al. [107],
et al. (b) (b)
[107], Li et 18
Lial. of
al.31[108],
et [108], andand
(c)
Tipplook et al. [109].
(c) Tipplook et al. [109].

Figure 12. Figure 12. Schematic

Schematic diagrams of diagrams of the in-solution
the in-solution plasma
plasma systems systems by
proposed proposed byal.
(a) Lee et (a)[91]
Leeand
et al.(b)
[91]
Li et al. [110].
and (b) Li et al. [110].
Lee et al. selected a pair of tungsten electrodes with a diameter of 0.8 mm, covered with
an insulating
Panomsuwan ceramic
et al. also used atube.
pair The electrodes
of tungsten were placed
electrodes 1 mm in the center of the
in diameter. TheTeflon reactor
electrodes were covered with an insulating ceramic tube, and had a gap of 1 mm. The conditions
with a gap distance of 1.0 mm (Figure 11a). The optimized applied voltage
bipolar powerofsource
in-solution
used hadplasma were
a pulse found to
duration of be 0.5μsµs,
0.80 100a frequency
and kHz, and 2ofkV 20for theIn-
kHz. pulse duration,
pulse
solution plasma was repetition
initiated frequency,
and stablyand voltage, inside
maintained respectively.
100 mLIn-solution plasma was produced
of liquid precursor
under vigorousfrom various
stirring solvents—such
(Figure as carbon, nitrogen,
10b). Cyano-aromatic molecules and boron precursors—for
(2-cyanopyridine, cyan- synthesizing
boron–carbon–nitrogen
opyrazine) were nanoparticles
used as liquid precursors [107]. of nitrogen-doped carbon NPs
for the synthesis
(NCNPs) [105]. Li et al. employed a pair of tungsten electrodes with a diameter of 1 mm as the
Morishitapowered electrode
et al. also employed and grounded
tungsten electrode.
electrodes 1 mmThese electrodes
in diameter forwere placed at the center
in-solution
of a glass reactor with a gap distance of 0.5 mm. To ignite
plasma. The electrodes were covered with a ceramic segment, and the distance between the plasma discharge of the
them was set in-solution
to 0.5 mm. plasma system,
The applied power
voltage was
was applied
about by using
1.7 kV, a bipolarfrequency
the repetition pulse with a voltage of
was 15 kHz, and the pulse width was 1.0 μs. The precursors for the fast formation of
nanocarbons were hexane, hexadecane, cyclohexane, and benzene. For the extraction of
nanocarbons, plasma-treated precursors were dried at 100 ℃ in an oven (Figure 10c) [106].
Lee et al. selected a pair of tungsten electrodes with a diameter of 0.8 mm, covered
with an insulating ceramic tube. The electrodes were placed in the center of the Teflon
reactor with a gap distance of 1.0 mm (Figure 11a). The optimized applied voltage condi-
Polymers 2021, 13, 2267 17 of 28

2.0 kV. The pulse duration and repetition frequency were 1 µs and 20 kHz, respectively
(Figure 11b). NCNPs were synthesized from pyrazine and acrylonitrile [108].
Tipplook et al. used in-solution plasma as an in situ system for the synthesis of
amino-rich nanocarbons. This system had a pair of tungsten rods with a diameter of
1 mm as the powered and grounded electrodes. The electrodes were covered with an
insulating tube, inserted into a silicone stopper, and placed at the center of the glass reactor,
1 mm apart. The glass reactor (Figure 11c) contained 100 mL of a liquid precursor (phenol,
(3-aminopropyl)triethoxysilane, and ethanol). Then, a HV bipolar pulse power with a
voltage of 4kV, a pulse duration of 1 µs, and a repetition frequency of 15 kHz was applied
through the electrodes to generate the in-solution plasma [109].
Lee et al. chose an in-solution plasma system with an asymmetrical pair of tungsten
needle electrodes. The diameter of the anode was 1.5 mm, and the gap between the
electrodes was 5 mm. Five capacitors with a capacitance of 0.1 µF were connected in
parallel, and the capacitors with equivalent capacitance of 0.5 µF were charged by a
positive-polarity DC power supply with a maximum charging voltage of 19 kV (Figure 12a).
Titanium tetraisopropoxide dissolved in ethanol (Ti-contained solution) was used as a
liquid precursor to synthesize carbon-incorporated titanium oxide nanocrystals [91].
Alsaeedi et al. reported that nanocarbons were successfully synthesized by using in-
solution plasma. In this paper, the in-solution plasma was generated between two carbon
electrodes. The carbon rod electrodes each had a diameter of 3 mm, and were separated by
a gap of 1 mm. The electrodes were immersed in 50 mL of ethanol (Figure 12b), and the
pulse voltage, frequency, and pulse width were 4 kV, 30 kHz, and 4 µs, respectively [110].
Shin et al. [111,112] added a gas bubble to the in-solution plasma system. The gas
bubble was often used as a plasma channel to enhance in-solution plasma performance in
pulsed discharge systems [111]. In a cylindrical glass reactor, the two tungsten electrodes
were oriented 1 mm apart, and were positioned in the capillary glass tube for the Ar gas
channel. The Ar gas was introduced along with two electrodes in parallel [111], thus
forming a gas bubble channel between the electrodes. The gap between the glass capillaries
was 3 mm. The plasma discharge was generated in a gas bubble between the electrodes in
an aniline monomer acting as the liquid precursor (Figure 13a). A bipolar pulse with an
amplitude of 16.4 kV and a frequency of 5 kHz was used to generate the in-solution plasma
within the Ar bubble channel, and the bipolar pulse duty ratio was 60 µs [111].
Additionally, Shin et al. [112] also used an asymmetrical electrode structure: the
tungsten electrode was placed in a quartz tube for the Ar gas inlet, where its diameter
was 0.5 mm and its exact position extruded 1 mm from the end of the capillary quartz
tube. On the other hand, a cylindrical copper electrode with a 5 mm width was wrapped
around the outside surface of the quartz tube. The copper electrode was positioned 3 mm
away from the end of the capillary quartz tube. There were two capillary tubes, with a
separation distance of 2 mm. The plasma channel was formed from Ar gas with a flow
rate of 100 sccm. A bipolar pulse with a voltage of 16 kV, a frequency of 5 kHz, and a
pulse width of 100 µs was employed to generate the in-solution plasma (Figure 13b) [112].
Table 4 displays a summary of this subsection.
 were oriented 1 mm apart, and were positioned in the capillary glass tube for the Ar gas
channel. The Ar gas was introduced along with two electrodes in parallel [111], thus form-
ing a gas bubble channel between the electrodes. The gap between the glass capillaries
was 3 mm. The plasma discharge was generated in a gas bubble between the electrodes
Polymers 2021, 13, 2267
in an aniline monomer acting as the liquid precursor (Figure 13a). A bipolar pulse with an
18 of 28
amplitude of 16.4 kV and a frequency of 5 kHz was used to generate the in-solution
plasma within the Ar bubble channel, and the bipolar pulse duty ratio was 60 μs [111].

Figure13.
Figure Schematicdiagrams
13.Schematic diagramsofof the
the in-solution
in-solution plasma
plasma system
system with
with a gas
a gas channel
channel proposed
proposed by by
(a,b)
(a,b)Shin
Shinetetal.
al.[111,112].
[111,112].

Table 4. Summary of syntheses using in-solution plasma methods.

Electrode Author
No NPs Precursor Plasma Source Year
(Gap) Reference
Nitrogen–carbon Tungsten Bipolar Pulse Hyun et al.
1 N-methyl-2-pyrrolidone 2016
nanosheets (NCNS) (1 mm) (2 kV, 25–200 kHz, 1 µs) [103]
2-Pyrrolidone,
Tungsten 1-methylpyrrolidine, pyrrolidine, Bipolar Pulse Hyun et al.
2 NCNS 2017
(1 mm) pyrrole, cyclopentanone, and (2 kV, 200 kHz, 1 µs) [104]
cyclohexanone
Nitrogen-doped
Tungsten Bipolar Pulse Panomsuwan et al.
3 carbon nanoparticles Cyanopyridine, cyanopyrazine 2016
(1 mm) (20 kHz, 0.8 µs) [105]
(NCNPs)
Tungsten Hexane, hexadecane, cyclohexane, Bipolar Pulse Morishita et al.
4 Nanocarbons 2016
(0.5 mm) benzene (1.7 kV, 15 kHz, 1 µs) [106]
Boron–carbon–
Tungsten Pyridine, B-tribromoborazine, Bipolar Pulse Lee et al.
5 nitrogen 2017
(1 mm) boric acid (2 kV, 100 kHz, 0.5 µs) [107]
nanocarbons
Tungsten Bipolar Pulse Li et al.
6 Carbon Pyrazine, acrylonitrile 2016
(0.5 mm) (2 kV, 20 kHz, 1 µs) [108]
Phenol
Amino-modified Tungsten Bipolar Pulse Tipplook et al.
7 (3-aminopropyl)triethoxysilane 2020
nanocarbon (1 mm) (4 kV, 15 kHz, 1 µs) [109]
(APTES)
Carbon TiOX/carbon Tungsten DC Lee et al.
8 Ti-contained solution 2015
composite nanosheets (5 mm) (19 kV) [91]
Polymers 2021, 13, 2267 19 of 28

Table 4. Cont.

Electrode Author
No NPs Precursor Plasma Source Year
(Gap) Reference
Carbon Pulse Alsaeedi et al.
9 Carbon, Pt–carbon Ethanol 2019
(1 mm) (4 kV, 30 kHz, 4 µs) [110]
Tungsten Bipolar Pulse Shin et al.
10 Polyaniline Aniline
(1 mm) (16.4 kV, 5 kHz, 60 µs) [111]
Tungsten–copper Bipolar Pulse Shin et al.
11 Polyaniline Aniline
(4 mm) (16 kV, 5 kHz, 100 µs) [112]

4. Plasma Polymerization
4.1. Synthesis of Polymers Using Plasma Techniques
Plasma polymerization accompanies complex physicochemical reactions that are
very different from conventional chemical polymerization methods. In plasma poly-
merization, monomer molecules are broken into electrons, ions, radicals, and excited
molecules through collisions with energetic electrons. A resulting polymer then grows
by random recombination among these particles. Figure 14a shows the mechanisms of
plasma polymerization [113]; Figure 14b is a scheme of a general plasma polymerization
system with these mechanism stages [114]. A polymer is synthesized onto a solid phase
through recombination, where single or divalent reactive species generated by plasma are
polymerized (recombination) by the reactions between reactive species and monomers
(Reactions (1) and (4)) or between the reactive species (Reactions (2), (3), and (5)) [113,114].
Indeed, plasma polymerization is a competitive process between formation by synthesis of
polymer-forming species and ablation of the polymer film itself [115]. Unlike conventional
chemical polymerization methods—such as self-assembly, layer-by-layer, or spin coating—
a continuous fragmentation and random recombination easily creates the high cross-linking
property that is characteristic of plasma polymers, as shown in Figure 14c [116]. The high
cross-linking property of plasma polymers is responsible for providing better mechanical
stability and less morphological changes [74,114,117].

4.2. Characterization and Chemical Structure of the Polymerized Films Obtained Using
APP Techniques
In general, the reaction mechanism of plasma polymerization is mainly established
in a vacuum state or low-pressure conditions. In APP methods, the reaction scheme of
plasma polymerization is not yet verified, and the related underlying mechanisms are
under-studied. Nevertheless, the detailed reaction mechanism of APP polymerization
can be confirmed by clearly identifying the chemical structures of polymerized films via
characterization methods such as Fourier transform infrared spectroscopy (FT-IR), nuclear
magnetic resonance (NMR), and X-ray photoelectron spectroscopy (XPS). The results of
this analysis can be seen in Figure 15, where Asandulesa et al. reported a polymerization
mechanism by identifying the chemical structures of the polymer films through the charac-
terization of APP-polymerized films synthesized from various monomers [118]. In the case
of the benzaldehyde-based polymer films, the polymerized films showed two different
types of chemical structures, depending on the plasma conditions: The first type was where
the aromatic ring was preserved during the APP polymerization; in this case, reactions of
benzaldehyde were initiated by breaking the π bonds from aldehyde, which was confirmed
by the presence of C–O bonds in the polymeric film through FT-IR and XPS spectra, as
shown in Figure 15a. The second type was where the aromatic ring was broken during the
APP polymerization; in this case, aliphatic functional groups were likely obtained from
the aromatic ring breakage during plasma polymerization, and aliphatic hydrocarbons
(CH2 and CH3 protons) were also produced by hydrogenation reactions—which was con-
firmed through FT-IR and NMR spectra, as shown in Figure 15b,c. Finally, the reactive
species were shown to randomly recombine, and the polymeric film was obtained via the
reactions between radical species during the APP polymerization, as shown in Figure 15d.
The reactive species could also be oxidized during film growth, producing functional
Polymers 2021, 13, 2267 20 of 28

groups such as ethers, alcohols, and esters—which was confirmed by the presence of ethers,
alcohol, esters, and carbonate units in the chemical composition of the polymeric film
identified from FT-IR and XPS data, as shown in Figure 15e [118]. In summary, the APP
Polymers 2021, 13, x polymerization mechanism, from a chemical point of view, is related to the formation
22 of 31 of
benzaldehyde-based polymer films, as illustrated in Figure 16.

Polymers 2021, 13, x 23 of 31

functional groups such as ethers, alcohols, and esters—which was confirmed by the pres-
Figure
ence
Figure 14.14.
of(a) Mechanisms
ethers, of esters,
alcohol,
(a) Mechanisms plasma polymerization
and carbonate
of plasma [113]. (b)
units
polymerization A[113].
in the scheme of A
chemical
(b) acomposition
general
schemeplasma
of aofgeneral
the pol-plasma
polymerization
ymeric film system [114].from
identified (c) Comparison
FT-IR and of a conventional
XPS data, as shownpolymer
in (left) 15e
Figure and [118].
plasmaInpolymer
summary,
polymerization system [114]. (c) Comparison of a conventional polymer (left) and plasma polymer
(right), derived from equivalent monomers [116].
the APP
(right), polymerization
derived mechanism,
from equivalent monomersfrom a chemical point of view, is related to the for-
[116].
mation of benzaldehyde-based polymer films, as illustrated in Figure 16.
4.2. Characterization and Chemical Structure of the Polymerized Films Obtained Using APP
Techniques
In general, the reaction mechanism of plasma polymerization is mainly established
in a vacuum state or low-pressure conditions. In APP methods, the reaction scheme of
plasma polymerization is not yet verified, and the related underlying mechanisms are un-
der-studied. Nevertheless, the detailed reaction mechanism of APP polymerization can be
confirmed by clearly identifying the chemical structures of polymerized films via charac-
terization methods such as Fourier transform infrared spectroscopy (FT-IR), nuclear mag-
netic resonance (NMR), and X-ray photoelectron spectroscopy (XPS). The results of this
analysis can be seen in Figure 15, where Asandulesa et al. reported a polymerization
mechanism by identifying the chemical structures of the polymer films through the char-
acterization of APP-polymerized films synthesized from various monomers [118]. In the
case of the benzaldehyde-based polymer films, the polymerized films showed two differ-
ent types of chemical structures, depending on the plasma conditions: The first type was
where the aromatic ring was preserved during the APP polymerization; in this case, reac-
tions of benzaldehyde were initiated by breaking the π bonds from aldehyde, which was
Figure
Figure 15. Chemical
15. Chemical structures
structures identified
confirmed
identified viacharacterization
by via
the characterization
presence of C–O ofofbenzaldehyde-based
bonds polymer
in the polymeric
benzaldehyde-based films
film
polymer usingusing
through
films APP techniques,
FT-IRAPPandtechniques,
XPS
where (a) depicts benzaldehyde
spectra, radical
as generation
shown in by π15a.
Figure bondThebreakage
second from
type aldehyde,
was where(b) depicts
the aliphatic
aromatic chain
ring was produc-
broken
wheretion
(a) depicts benzaldehyde radical
by aromatic ring breakage,
generation
(c) depicts
by π bond breakage
hydrogenation ofinthe
from
aliphatic
aldehyde, (b) depicts
chain, (d)functional
aliphatic
depicts thegroups
recombination
chain production
process
by aromatic during the APP polymerization; this case, aliphatic wereprocess
likely ob-
betweenring breakage, radicals
benzaldehyde (c) depicts
and hydrogenation
aliphatic chains, of
andthe
(e)aliphatic chain,
depicts benzaldehyde(d) depicts
radicalthe recombination
oxidation under plasma between
condi-
tained from the aromatic ring breakage during plasma polymerization, and aliphatic hy-
benzaldehyde
tions [118].radicals and aliphatic chains, and (e) depicts benzaldehyde radical oxidation under plasma conditions [118].
drocarbons (CH2 and CH3 protons) were also produced by hydrogenation reactions—
which was confirmed through FT-IR and NMR spectra, as shown in Figure 15b,c. Finally,
the reactive species were shown to randomly recombine, and the polymeric film was ob-
tained via the reactions between radical species during the APP polymerization, as shown
in Figure 15d. The reactive species could also be oxidized during film growth, producing
Figure 15. Chemical structures identified via characterization of benzaldehyde-based polymer films using APP techniques,
where (a) depicts benzaldehyde radical generation by π bond breakage from aldehyde, (b) depicts aliphatic chain produc-
tion by aromatic ring 13,
Polymers 2021, breakage,
2267 (c) depicts hydrogenation of the aliphatic chain, (d) depicts the recombination process 21 of 28
between benzaldehyde radicals and aliphatic chains, and (e) depicts benzaldehyde radical oxidation under plasma condi-
tions [118].

Figure
Figure 16. APP 16. APP polymerization
polymerization mechanisms,
mechanisms, from from
a chemical a chemical
point point oftoview,
of view, related related toofthe
the formation for-
benzaldehyde-based
mation
polymer films. of benzaldehyde-based polymer films.

5. Main Properties
5. Mainand Current Applications
Properties of the Polymers
and Current Applications Obtained
of the Polymers viaObtained
APP via
PolymerizationAPP Polymerization
The technicalThestate of APP state
technical polymerization is sufficientlyisenhanced
of APP polymerization to enhanced
sufficiently synthesizetoa synthesize a
conducting polymer filmpolymer
conducting with single-
filmand
withpolycrystalline properties (Figure
single- and polycrystalline 17a,b)(Figure
properties [62]. 17a,b) [62].
These advanced APP
These polymerization
advanced techniques are techniques
APP polymerization actively investigated
are activelyfor investigated
various ap- for various
applications;
plications; functional functional
coatings are onecoatings are one such
such representative representative
application of APP application
polymeri-of APP poly-
zation. Plasmamerization. Plasma
polymerization polymerization
can can change
change the wettability the wettability
of any of any surface to demon-
surface to demonstrate
strate hydrophobic/philic
hydrophobic/philic characteristics,
characteristics, depending depending
on the amount on the
of polar amount of
or nonpolar polar or nonpo-
func-
lar functional groups on the coating’s surface [78,81]. Therefore,
tional groups on the coating’s surface [78,81]. Therefore, the properties of functional coat- the properties of func-
tional coatings
ings are commonly are commonly
determined determined
from the kinds from the
of materials kinds
used. of example,
For materials TMS,
used. For example,
TMS, APDMES, HMDSO, AA, and PMA are utilized for wettable coatings (hydrophilic/phobic)
(Figure 17c,d) [57,67,71,73,78,81]. In a biological application, Getnet et al. [72] and St’ahel et al. [77]
investigated whether polymer films synthesized via APP polymerization could be ap-
plied for antibacterial properties (Figure 18a,b) [72,77]. As shown in Figure 14c [116], the
plasma polymers have the high cross-linking property resulting from continuous fragmen-
tation and random recombination during plasma polymerization; that is, the polymers
obtained using plasma techniques show better mechanical stability and fewer morphologi-
cal changes [74,114,117]. Bardon et al. [74] reported that the DOCA polymer coatings were
modified by adding HdiA or HdiMA to the DOCA precursor, and the related mechanical
reinforcement was examined (Figure 18c) [74]. Abessolo et al. [82] also reported that the
dielectric constant of polymer films deposited by APP could be lowered by varying the
monomer precursors used—i.e., siloxane and silazane—as well as by varying their ring size
(Figure 18d) [82]. Additionally, the surface morphology of the polymers obtained using
APP polymerization shows rough or porous films, thereby enhancing their sensing capa-
bility as gas sensors. A porous polythiophene prepared via APP polymerization showed
outstanding response properties as a NO2 gas sensor when compared to polythiophene
synthesized via chemical methods (Figure 18e) [119].
 ported that the dielectric constant of polymer films deposited by APP could be lowered
by varying the monomer precursors used—i.e., siloxane and silazane—as well as by var-
ying their ring size (Figure 18d) [82]. Additionally, the surface morphology of the poly-
mers obtained using APP polymerization shows rough or porous films, thereby enhanc-
Polymers 2021, 13, 2267 ing their sensing capability as gas sensors. A porous polythiophene prepared via22APPof 28
polymerization showed outstanding response properties as a NO2 gas sensor when com-
pared to polythiophene synthesized via chemical methods (Figure 18e) [119].

Figure 17.
17. Transmission
Transmissionelectron
electronmicroscopy
microscopy(TEM)
(TEM) images
imagesof of
polypyrrole NPsNPs
polypyrrole with (a) single-
with (a) single-
Polymers 2021, 13, x crystalline and
and (b)
(b) polycrystalline
polycrystallineproperties
properties[62].
[62].(c)
(c)Superhydrophobicity
Superhydrophobicityofofthe
thecoated
coatedfilms 25
films ofthe
onon 31
the cotton fabrics [67]. (d) Hydrophilization of the surface of polypropylene
cotton fabrics [67]. (d) Hydrophilization of the surface of polypropylene [73]. [73].

Figure 18. (a,b) Antibacterial properties created by APP polymerization [72,77]. (c) Scratch tracks for coatings of DOCA,
Figure 18. (a,b) Antibacterial properties created by APP polymerization [72,77]. (c) Scratch tracks
HdiA and HdiMA films [74]. (d) Estimation of the dielectric constant of insulating layers made by cyclic organosilicons [82].
for coatings of DOCA, HdiA and HdiMA films [74]. (d) Estimation of the dielectric constant of in-
(e) NO2 -sensing properties sulating
of a polythiophene
layers madefilm
byprepared using the APPJ
cyclic organosilicons technique
[82]. [119].
(e) NO2-sensing properties of a polythiophene
film prepared using the APPJ technique [119].
Polymers 2021, 13, 2267 23 of 28

6. Conclusions and Future Perspectives

In summary, the plasma synthesis of polymer films and NPs under atmospheric
pressure has become an advanced and replicated method, due to the various experimental
advantages of this kind of synthesis, such as simplified equipment, faster processes, lower
thermal temperatures, lower costs, and eco-friendly waste. In this review, we presented the
recent studies on the synthesis of polymer films and NPs using the various APP methods.
These methods are categorized into two types, depending on the state of the precursor:
The APP methods using a gas/aerosol-phase precursor are almost always used for a
polymer deposition or coating. The APP methods using liquid-type precursors are more
favorable for the formation of NPs. First, we described and summarized various GATP
methods that are employed as synthesis methods for polymer films. These methods all
successfully form polymer films via variations in the specific GATP techniques by varying
experimental parameters, such as the structure of the electrodes, types of precursors, types
of discharge gas, and discharge power sources (frequency, voltage, duty cycle). Next, this
review provided a summary and discussion of various liquid-plasma techniques used
primarily for the formation of NPs via non-thermal plasma interactions with various liquids,
including water or organic monomer solutions. Again, a wide range of NP synthesis can
be successfully achieved using liquid-plasma systems with various configurations of
electrodes, materials, and plasma power sources.
In the near future, various APP polymer synthesis methods will likely become ideal
candidates for industrial applications due to their potential for scaling-up while retaining
a practical and sustainable environment for synthesis. However, there remain some chal-
lenges for applications of these APP methods, i.e., the low plasma density of APP and the
potential for using a large amount of the gas source in some cases. Thus, it is important to
incentivize and support further investigations and research on novel APP polymerization
and synthesis methods in order to continue to overcome these challenges and accomplish
large-scale polymer film deposition or mass production of NPs with stable discharge under
open-air conditions.

Author Contributions: H.J.J., E.Y.J., H.-S.T. and C.-S.P. contributed to the conception. H.J.J., E.Y.J.,
H.-S.T. and C.-S.P. reviewed references and wrote the draft of the manuscript. The authors con-
tributed equally review and editing. All authors have read and agreed to the published version of
the manuscript.
Funding: This research was supported by the National Research Foundation of Korea (NRF) grant
funded by the South Korean government (MOE) (No. 2020R1I1A3071693).
Institutional Review Board Statement: Not applicable.
Informed Consent Statement: Not applicable.
Data Availability Statement: Not applicable.
Conflicts of Interest: The authors declare no conflict of interest.

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Weinheim, Germany, 2021; pp. 337–375.
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