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 for polymer synthesis are rarely reported. We introduce and compile over 50 recent papers on various APP polymerization methods that allow us to discuss the existing challenges and future direction of GATP and solution plasma methods under ambient air conditions for large-area and mass nanoparticle production.

Although polymerized aniline (polyaniline, PANI) with and without iodine (I₂) doping has already been extensively studied, little work has been done on the synthesis of PANI films using atmospheric pressure plasma (APP) deposition. Therefore, this study characterized pure and I₂-doped PANI films synthesized using an advanced APP polymerization system. The I₂ doping was conducted ex-situ and using an I₂ chamber method following the APP deposition. The pure and I₂-doped PANI films were structurally analyzed using field emission scanning electron microscope (FE-SEM), atomic force microscope (AFM), X-ray Diffraction (XRD), Fourier transform infrared spectroscopy (FT-IR), X-ray photoelectron spectroscopy (XPS), and time of flight secondary ion mass spectrometry (ToF-SIMS) studies. When increasing the I₂ doping time, the plane and cross-sectional SEM images showed a decrease in the width and thickness of the PANI nanofibers, while the AFM results showed an increase in the roughness and grain size of the PANI films. Moreover, the FT-IR, XPS, and ToF-SIMS results showed an increase in the content of oxygen-containing functional groups and C=C double bonds, yet decrease in the C–N and C–H bonds when increasing the I₂ doping time due to the reduction of hydrogen in the PANI films via the I₂. To check the suitability of the conductive layer for polymer display applications, the resistance variations of the PANI films grown on the interdigitated electrode substrates were also examined according to the I₂ doping time.

New nanostructured conducting porous polythiophene (PTh) films are directly deposited on substrates at room temperature (RT) by novel atmospheric pressure plasma jets (APPJs) polymerization technique. The proposed plasma polymerization synthesis technique can grow the PTh films with a very fast deposition rate of about 7.0 μm·min⁻¹ by improving the sufficient nucleation and fragment of the thiophene monomer. This study also compares pure and iodine (I₂)-doped PTh films to demonstrate the effects of I₂ doping. To check the feasibility as a sensing material, NO₂-sensing properties of the I₂-doped PTh films-based gas sensors are also investigated. As a result, the proposed APPJs device can produce the high density, porous and ultra-fast polymer films, and polymers-based gas sensors have high sensitivity to NO₂ at RT. Our approach enabled a series of processes from synthesis of sensing materials to fabrication of gas sensors to be carried out simultaneously.

This work researched polymerization of liquid aniline monomer by solution plasma with a gas bubble channel and investigated characteristics of solution plasma and polyaniline (PANI). The injected gas bubble channel in the proposed solution plasma process (SPP) played a significant role in producing a stable discharge in liquid aniline monomer at a low voltage and furthermore enhancing the contact surface area between liquid aniline monomer and plasma, thereby achieving polymerization on the boundary of the liquid aniline monomer and plasma. Solution plasma properties were analyzed with voltage–current, optical emission spectroscopy, and high-speed camera. Conductivity, percentage yield, and firing voltage of PANI nanoparticle dispersed solution were measured. To investigate the characteristics of synthesized PANI nanoparticles, field emission scanning electron microscopy, dynamic light scattering, transmission electron microscopy, selective area electron diffraction (SAED) pattern, Fourier transform infrared spectroscopy (FTIR), gel permeation chromatography, ¹H-nuclear magnetic resonance (¹H-NMR), and X-ray photo spectroscopy (XPS) were examined. The FTIR, ¹H-NMR, and XPS analysis showed the PANI characteristic peaks with evidence that some quinoid and benzene rings were broken by the solution plasma process with a gas bubble channel. The results indicate that PANI nanoparticles have a spherical shape with a size between 25 and 35 nm. The SAED pattern shows the amorphous pattern.

Pinhole free layers are needed in order to prevent oxygen and water from damaging flexible electrical and bio-devices. Although polymerized methyl methacrylate (polymethyl methacrylate, PMMA) for the pinhole free layer has been studied extensively in the past, little work has been done on synthesizing films of this material using atmospheric pressure plasma-assisted electro-polymerization. Herein, we report the synthesis and properties of plasma-PMMA (pPMMA) synthesized using the atmospheric pressure plasma-assisted electro-polymerization technique at room temperature. According to the Fourier transform infrared spectroscopy (FT-IR), X-ray photoelectron spectroscopy (XPS), and time of flight-secondary ion mass spectrometry (ToF-SIMS) results, the characteristic peaks from the pPMMA polymer chain were shown to have been detected. The results indicate that the percentage of hydrophobic groups (C–C and C–H) is greater than that of hydrophilic groups (C–O and O–C=O). The field emission-scanning electron microscope (FE-SEM) and thickness measurement results show that the surface morphology is quite homogenous and amorphous in nature, and the newly proposed pPMMA film at a thickness of 1.5 µm has high transmittance (about 93%) characteristics. In addition, the results of water contact angle tests show that pPMMA thin films can improve the hydrophobicity.

In-situ iodine (I₂)-doped atmospheric pressure (AP) plasma polymerization is proposed, based on a newly designed AP plasma reactor with a single wire electrode that enables low-voltage-driven plasma polymerization. The proposed AP plasma reactor can proceed plasma polymerization at low voltage levels, thereby enabling an effective in-situ I₂ doping process by maintaining a stable glow discharge state even if the applied voltage increases due to the use of a discharge gas containing a large amount of monomer vapors and doping materials. The results of field-emission scanning electron microscopy (FE-SEM) and Fourier transformation infrared spectroscopy (FT-IR) show that the polyaniline (PANI) films are successfully deposited on the silicon (Si) substrates, and that the crosslinking pattern of the synthesized nanoparticles is predominantly vertically aligned. In addition, the in-situ I₂-doped PANI film fabricated by the proposed AP plasma reactor exhibits excellent electrical resistance without electrical aging behavior. The developed AP plasma reactor proposed in this study is more advantageous for the polymerization and in-situ I₂ doping of conductive polymer films than the existing AP plasma reactor with a dielectric barrier.